KR20220111291A - Methods for preparing polysiloxazanes and methods of using polysiloxazanes for preparing amino-functional polyorganosiloxanes - Google Patents

Abstract

Methods for preparing cyclic polysiloxazanes are disclosed. Cyclic polysiloxazanes can optionally be converted to α-alkoxy-ou-amino-functional polysiloxanes. Cyclic polysiloxazanes or α-alkoxy-oo-amino-functional polysiloxanes can be used as capping agents for silanol-functional polyorganosiloxanes in a process for preparing amino-functional polyorganosiloxanes.

Description

Methods for preparing polysiloxazanes and methods of using polysiloxazanes for preparing amino-functional polyorganosiloxanes

Cross-reference to related applications

This application is filed under 35 U.S.C. Claims the benefit of U.S. Provisional Patent Application No. 62/940414, filed on November 26, 2019 under §119(e). U.S. Provisional Patent Application No. 62/940414 is incorporated herein by reference.

technical field

An improved method for preparing cyclic polysiloxazanes via the hydrosilylation reaction of an allyl-functional amine with a SiH terminated siloxane oligomer uses a hydrosilylation reaction promoter. Cyclic polysiloxazanes are useful for capping silanol groups in silanol-functional polyorganosiloxanes. Cyclic polysiloxazanes, and/or α-alkoxy-ω-amino-functional polysiloxanes prepared therefrom, can be used to prepare amino-functional polyorganosiloxanes.

Amino-functional polyorganosiloxanes, such as amine-terminated polydiorganosiloxanes, are useful for personal care applications such as hair care. Amine-terminated polydiorganosiloxanes may be useful, for example, in hair conditioning applications. Amine-terminated polydiorganosiloxanes prepared by condensation may suffer from the drawbacks of instability exhibited by viscosity changes and/or ammonia odor generation after aging, which is undesirable for personal care applications. Traditionally, primary amine terminated polyorganosiloxanes are expensive to prepare by equilibration because they require expensive starting materials and catalysts and require multiple process steps to complete.

Another method for preparing amine-terminated polyorganosiloxanes uses allylamine, or derivatives that hydrolyze to allylamine. They are used to form amine-terminated polyorganosiloxanes by performing hydrosilylation chemistry with SiH-terminated polymers; This method suffers from the disadvantage that the amine-terminated polyorganosiloxane product may contain at least trace amounts of SiH or allylamine, and after removal of either of these, the product may be used in any personal care application.

Another method for preparing amine-terminated polyorganosiloxanes is by ammonia decomposition of chloropropyl terminated siloxanes. This expensive multi-step process can suffer from the disadvantage of leaving residual salts (i.e., ammonium chloride) in the amine-terminated polyorganosiloxane product that can require extensive washing to remove, which is costly and Sustainability is poor. In addition, any residual ammonium chloride can create malodors, which is undesirable for personal care applications.

Challenges to be solved

New methods of making amino-functional polyorganosiloxanes that minimize or eliminate one or more of the above disadvantages are desired.

A process for preparing cyclic polysiloxazanes involves the hydrosilylation reaction of an allyl-functional amine with an SiH-terminated siloxane oligomer in the presence of a hydrosilylation reaction catalyst and a hydrosilylation reaction promoter. Cyclic polysiloxazanes can be used as capping agents for silanol-functional silanes and/or silanol-functional polyorganosiloxanes to prepare amino-functional silanes and/or amino-functional polyorganosiloxanes .

Part I. Synthesis of cyclic polysiloxazanes

A method for preparing a cyclic polysiloxazane comprises the following steps:

One)

a) allyl-functional amines;

b) a platinum catalyst capable of catalyzing the hydrosilylation reaction, and

의 하이드로실릴화 반응 촉진제(하이드로카르빌옥시-작용성 다이하이드로카르빌실란)(여기서,

는 이중 결합 및 삼중 결합으로 이루어진 군으로부터 선택되는 결합을 나타내고, 하첨자 a는 1 또는 2이고, 하첨자 b는 0 또는 1이되, 단

가 이중 결합인 경우 a = 2 및 b = 1이고,

가 삼중 결합인 경우 a = 1 및 b = 0이고; 각각의 R¹은 수소, 1 내지 15개의 탄소 원자의 알킬 기, 및 6 내지 20개의 탄소 원자의 아릴 기로 이루어진 군으로부터 독립적으로 선택되고; R²는 수소, 1 내지 15개의 탄소 원자의 알킬 기, 및 6 내지 20개의 탄소 원자의 아릴 기로 이루어진 군으로부터 선택되고; R³은 수소, 1 내지 15개의 탄소 원자의 알킬 기, 및 6 내지 20개의 탄소 원자의 아릴 기로 이루어진 군으로부터 선택되고; R⁴는 수소, 1 내지 15개의 탄소 원자의 알킬 기, 및 6 내지 20개의 탄소 원자의 아릴 기로 이루어진 군으로부터 선택되고; R⁵는 1 내지 15개의 탄소 원자의 독립적으로 선택된 1가 탄화수소 기이고; R⁶은 1 내지 15개의 탄소 원자의 독립적으로 선택된 1가 탄화수소 기임)를 포함하는 출발 재료들을 조합하여,c) chemical formula

Hydrosilylation reaction accelerator (hydrocarbyloxy-functional dihydrocarbylsilane) of

represents a bond selected from the group consisting of a double bond and a triple bond, the subscript a is 1 or 2, and the subscript b is 0 or 1, provided that

is a double bond, then a = 2 and b = 1,

a = 1 and b = 0 when is a triple bond; each R ¹ is independently selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ² is selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ³ is selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ⁴ is selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ⁵ is an independently selected monovalent hydrocarbon group of 1 to 15 carbon atoms; R ⁶ is an independently selected monovalent hydrocarbon group of 1 to 15 carbon atoms;

forming a reaction mixture, and then

2) to the reaction mixture,

의 SiH-말단화된 실록산 올리고머(여기서, 각각의 R⁸은 1 내지 18개의 탄소 원자의 독립적으로 선택된 1가 탄화수소 기이고, 하첨자 x는 1 또는 2임)를 첨가하여, 환형 폴리실록사잔을 제조하는 단계.d) chemical formula

SiH-terminated siloxane oligomer of (wherein each R ⁸ is an independently selected monovalent hydrocarbon group of 1 to 18 carbon atoms and the subscript x is 1 or 2) to prepare a cyclic polysiloxazane step to do.

Starting material a) Allyl-functional amine

In the process for preparing cyclic polysiloxazanes, the starting material a) is an allyl-functional amine. Allyl-functional amines have the formula:

을 가질 수 있으며, 여기서 각각의 R⁹는 수소 및 1 내지 15개의 탄소 원자, 대안적으로 1 내지 12개의 탄소 원자, 대안적으로 1 내지 6개의 탄소 원자의 알킬 기로 이루어진 군으로부터 독립적으로 선택된다. 적합한 알킬 기는 메틸, 에틸, 프로필(예를 들어, 아이소-프로필 및/또는 n-프로필), 부틸(예를 들어, 아이소부틸, n-부틸, tert-부틸 및/또는 sec-부틸), 펜틸(예를 들어, 아이소펜틸, 네오펜틸 및/또는 tert-펜틸), 헥실, 헵틸, 옥틸, 노닐 및 데실뿐만 아니라 사이클로펜틸 및 사이클로헥실과 같은 사이클로알킬 기를 포함하는 6개 이상의 탄소 원자의 분지형 포화 1가 하이드로카르빌 기로 예시된다. 대안적으로, R⁹에 대한 각각의 알킬 기는 메틸일 수 있다. 대안적으로, 각각의 R⁹는 수소 원자일 수 있다. 대안적으로, 분자당 적어도 하나의 R⁹는 알킬 기, 예컨대 메틸일 수 있다. 이론에 얽매이려는 것은 아니지만, 환형 폴리실록사잔은 실란올-작용성 실란 및 실란올-작용성 폴리오르가노실록산에 대한 캡핑제로서 사용되어, 각각의 R⁹가 수소 원자인 경우 1차 아민-작용성 실란 및 아민-작용성 폴리오르가노실록산을 제조할 수 있는 것으로 여겨진다.

wherein each R ⁹ is independently selected from the group consisting of hydrogen and an alkyl group of 1 to 15 carbon atoms, alternatively 1 to 12 carbon atoms, alternatively 1 to 6 carbon atoms. Suitable alkyl groups include methyl, ethyl, propyl (eg iso-propyl and/or n-propyl), butyl (eg isobutyl, n-butyl, tert-butyl and/or sec-butyl), pentyl ( branched saturated 1 of 6 or more carbon atoms, including cycloalkyl groups such as isopentyl, neopentyl and/or tert-pentyl), hexyl, heptyl, octyl, nonyl and decyl, as well as cyclopentyl and cyclohexyl 1 is exemplified by a hydrocarbyl group. Alternatively, each alkyl group for R ⁹ can be methyl. Alternatively, each R ⁹ may be a hydrogen atom. Alternatively, at least one R ⁹ per molecule may be an alkyl group such as methyl. Without wishing to be bound by theory, cyclic polysiloxazanes are used as capping agents for silanol-functional silanes and silanol-functional polyorganosiloxanes, such that a primary amine-functional when each R ⁹ is a hydrogen atom. It is believed that silane and amine-functional polyorganosiloxanes can be prepared.

Allyl-functional amines are known in the art and are commercially available. For example, allylamine, N-allyl-methylamine, N-allylcyclopentylamine, 2-methyl-allylamine and allylcyclohexylamine of the formula CH ₂ =CH-CH ₂ NH ₂ of the formula CH 2 =CH-CH 2 NH 2 St. Louis, MO, USA It is commercially available from Millipore Sigma of Alternatively, the allyl-functional amine may be an allylamine.

starting material b) platinum catalyst

In the process for preparing cyclic polysiloxazanes, the starting material b) is a platinum catalyst. Platinum catalysts are known in the art and are commercially available.

The platinum catalyst may be platinum metal. Alternatively, the platinum catalyst may contain platinum metal. Suitable platinum catalysts include bi) compounds of platinum metal, which may include chloroplatinic acid (Speier's Catalyst), chloroplatinic acid hexahydrate and platinum dichloride. Alternatively, the starting material b) may comprise a complex of the compound for b-ii) bi) with a low molecular weight organopolysiloxane or b-iii) a platinum compound microencapsulated in a matrix or core shell type structure. Complexes of platinum with low molecular weight organopolysiloxanes include 1,3--1,1,3,3-tetramethyl-divinyl-disiloxane complexes with platinum (Karstedt's Catalyst) and tetramethyltetravinylcyclo Platinum(0) complex in tetrasiloxane (Ashby's Catalyst). Alternatively, the hydrosilylation reaction catalyst may be a complex as described above b-iv) microencapsulated in a resin matrix. The platinum catalyst catalyzes the hydrosilylation reaction and/or silicon-nitrogen bonds from the starting material d), Si-H and nitrogen-hydrogen bonds from the starting material a), by dehydrogenation coupling of NH, Si-N and dihydrogen, H ₂ . Although platinum catalysts are described above, other platinum group metal hydrosilylation reaction catalysts may also be useful. This may include using a metal selected from rhodium, ruthenium, palladium, osmium and iridium. Alternatively, the hydrosilylation reaction catalyst may be a compound of such a metal, such as chloridotris(triphenylphosphane)rhodium(I) (Wilkinson's Catalyst), rhodium diphosphine chelates such as [1, 2-bis(diphenylphosphino)ethane]dichlorodirhodium or [1,2-bis(diethylphosphino)ethane]dichlorodirhodium.

Alternatively, starting material b), the hydrosilylation reaction catalyst comprises i) platinum metal, ii) a compound of platinum, iii) a complex of said compound with an organopolysiloxane, iv) said compound microencapsulated in a matrix or core shell type structure , v) said complexes of said compounds microencapsulated in a matrix or core-shell type structure, and vi) combinations of two or more thereof.

Exemplary hydrosilylation reaction catalysts are disclosed in U.S. Patent Nos. 3,159,601; 3,220,972; 3,296,291; 3,419,593; 3,516,946; 3,814,730; 3,989,668; 4,784,879; 5,036,117; and 5,175,325 and European Patent EP 0 347 895 B. Microencapsulated hydrosilylation reaction catalysts and methods for their preparation are known in the art, as exemplified in US Pat. Nos. 4,766,176 and 5,017,654. Hydrosilylation reaction catalysts are commercially available, for example SYL-OFF™ 4000 catalyst and SYL-OFF™ 2700 are available from Dow Silicones Corporation.

While the amount of catalyst useful herein will depend on a variety of factors, including the type and amount of other starting materials used in the process, the amount of catalyst is based on the total weight of all starting materials used in the process for preparing the cyclic polysiloxazane. It may be sufficient to provide 10 ppm to 500 ppm, alternatively 20 ppm to 100 ppm, alternatively 35 ppm to 60 ppm of Pt on the same basis.

starting material c) hydrosilylation reaction accelerator

In the process for preparing the cyclic polysiloxazane, the starting material c) is a hydrosilylation reaction accelerator. The starting material c) may be a hydrocarbyloxy-functional dihydrocarbylsilane. Hydrocarbyloxy-functional dihydrocarbylsilanes have the formula:

을 가질 수 있으며, 여기서

는 이중 결합 및 삼중 결합으로 이루어진 군으로부터 선택되는 결합을 나타내고, 하첨자 a는 1 또는 2이고, 하첨자 b는 0 또는 1이되, 단

가 이중 결합인 경우 a = 2 및 b = 1이고,

가 삼중 결합인 경우 a = 1 및 b = 0이고; 각각의 R¹은 수소, 1 내지 15개의 탄소 원자의 알킬 기, 및 6 내지 20개의 탄소 원자의 아릴 기로 이루어진 군으로부터 독립적으로 선택되고; R²는 수소, 1 내지 15개의 탄소 원자의 알킬 기, 및 6 내지 20개의 탄소 원자의 아릴 기로 이루어진 군으로부터 선택되고; R³은 수소, 1 내지 15개의 탄소 원자의 알킬 기, 및 6 내지 20개의 탄소 원자의 아릴 기로 이루어진 군으로부터 선택되고; R⁴는 수소, 1 내지 15개의 탄소 원자의 알킬 기, 및 6 내지 20개의 탄소 원자의 아릴 기로 이루어진 군으로부터 선택되고; R⁵는 1 내지 15개의 탄소 원자의 독립적으로 선택된 1가 탄화수소 기이고; R⁶은 1 내지 15개의 탄소 원자의 독립적으로 선택된 1가 탄화수소 기이다. 대안적으로, R⁵ 및 R⁶ 중 적어도 하나는 아릴 기일 수 있다. 대안적으로, R⁵ 및 R⁶ 둘 모두는 아릴 기이다.

can have, where

represents a bond selected from the group consisting of a double bond and a triple bond, the subscript a is 1 or 2, and the subscript b is 0 or 1, provided that

is a double bond, then a = 2 and b = 1,

a = 1 and b = 0 when is a triple bond; each R ¹ is independently selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ² is selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ³ is selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ⁴ is selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ⁵ is an independently selected monovalent hydrocarbon group of 1 to 15 carbon atoms; R ⁶ is an independently selected monovalent hydrocarbon group of 1 to 15 carbon atoms. Alternatively, at least one of R ⁵ and R ⁶ may be an aryl group. Alternatively, both R ⁵ and R ⁶ are aryl groups.

In the above formula, the alkyl group for R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be as described above for R ⁹ . Suitable aryl groups are cyclopentadienyl, phenyl, tolyl, xylyl, anthracenyl, benzyl, 1-phenylethyl, 2-phenylethyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl and naphthyl. A monocyclic aryl group may have 5 to 9 carbon atoms, alternatively 6 or 7 carbon atoms, alternatively 5 or 6 carbon atoms. A polycyclic aryl group may have from 10 to 17 carbon atoms, alternatively from 10 to 14 carbon atoms, alternatively from 12 to 14 carbon atoms. Alternatively, the aryl group may be phenyl. Alternatively, R ¹ , R ² and R ³ may each be hydrogen. Alternatively, R ⁴ may be selected from the group consisting of hydrogen and methyl.

에 의해 나타낸 결합은 이중 결합일 수 있고, R¹, R², R³, 및 R⁴는 각각 수소일 수 있다. 대안적으로, R⁵는 알킬 및 아릴로 이루어진 군으로부터 선택될 수 있고, R⁶은 아릴일 수 있다. 대안적으로, R⁵는 아릴일 수 있고, R⁶은 아릴일 수 있다. 대안적으로, R⁵는 메틸, 2,4,6-트라이메틸페닐 및 2,4,6-트라이아이소프로필페닐로 이루어진 군으로부터 선택될 수 있다. 대안적으로, R⁶은 2,4,6-트라이메틸페닐 및 2,4,6-트라이아이소프로필페닐로 이루어진 군으로부터 선택될 수 있다.Alternatively,

The bond represented by may be a double bond, and R ¹ , R ² , R ³ , and R ⁴ may each be hydrogen. Alternatively, R ⁵ may be selected from the group consisting of alkyl and aryl, and R ⁶ may be aryl. Alternatively, R ⁵ can be aryl and R ⁶ can be aryl. Alternatively, R ⁵ may be selected from the group consisting of methyl, 2,4,6-trimethylphenyl and 2,4,6-triisopropylphenyl. Alternatively, R ⁶ may be selected from the group consisting of 2,4,6-trimethylphenyl and 2,4,6-triisopropylphenyl.

에 의해 나타낸 결합은 삼중 결합일 수 있고, R¹, R² 및 R³은 각각 수소일 수 있다. 대안적으로, R⁴는 수소 및 알킬, 예를 들어 메틸로 이루어진 군으로부터 선택될 수 있다. 대안적으로, R⁵는 알킬 및 아릴로 이루어진 군으로부터 선택될 수 있고, R⁶은 아릴일 수 있다. 대안적으로, R⁵는 아릴일 수 있고, R⁶은 아릴일 수 있다. 대안적으로, R⁵는 메틸, 2,4,6-트라이메틸페닐 및 2,4,6-트라이아이소프로필페닐로 이루어진 군으로부터 선택될 수 있다. 대안적으로, R⁶은 2,4,6-트라이메틸페닐 및 2,4,6-트라이아이소프로필페닐로 이루어진 군으로부터 선택될 수 있다.Alternatively,

The bond represented by may be a triple bond, and R ¹ , R ² and R ³ may each be hydrogen. Alternatively, R ⁴ may be selected from the group consisting of hydrogen and alkyl, for example methyl. Alternatively, R ⁵ may be selected from the group consisting of alkyl and aryl, and R ⁶ may be aryl. Alternatively, R ⁵ can be aryl and R ⁶ can be aryl. Alternatively, R ⁵ may be selected from the group consisting of methyl, 2,4,6-trimethylphenyl and 2,4,6-triisopropylphenyl. Alternatively, R ⁶ may be selected from the group consisting of 2,4,6-trimethylphenyl and 2,4,6-triisopropylphenyl.

Alternatively, the starting material c), the accelerator may be selected from the group consisting of:

(1,1,-다이메틸-2-프로페닐)옥시다이페닐실란,

(1-메틸-2-프로페닐)옥시다이페닐실란,

(1,1,-dimethyl-2-propenyl)oxydiphenylsilane,

(1-methyl-2-propenyl) oxydiphenylsilane,

트랜스-(3-페닐-2-프로페닐)옥시다이메틸실란,

(1-메틸-2-프로페닐)옥시다이메틸실란),

(1,1-다이메틸-2-프로페닐)옥시다이메틸실란),

알릴옥시-다이메틸실란,

알릴옥시-다이페닐실란,

알릴옥시-비스(2,4,6-트라이메틸페닐)실란,

알릴옥시-메틸-(2,4,6-트라이-아이소프로필페닐)실란, 및

trans- (3-phenyl-2-propenyl)oxydimethylsilane,

(1-methyl-2-propenyl)oxydimethylsilane),

(1,1-dimethyl-2-propenyl)oxydimethylsilane),

allyloxy-dimethylsilane,

allyloxy-diphenylsilane,

allyloxy-bis(2,4,6-trimethylphenyl)silane,

allyloxy-methyl-(2,4,6-tri-isopropylphenyl)silane, and

(1-메틸-2-프로핀-1-일)옥시다이페닐실란. 대안적으로, 출발 재료 c)는 하이드로카르빌옥시-작용성 아릴실란, 예컨대 (1,1-다이메틸-2-프로페닐)옥시다이페닐실란; (1-메틸-2-프로페닐)옥시다이페닐실란; 알릴옥시-다이페닐실란; 알릴옥시-비스(2,4,6-트라이메틸페닐)실란; 알릴옥시-메틸-(2,4,6-트라이-아이소프로필페닐)실란; 및/또는 (1-메틸-2-프로핀-1-일)옥시다이페닐실란일 수 있다. 대안적으로, 출발 재료 c), 촉진제는 알릴옥시-비스(2,4,6-트라이메틸페닐)실란; 알릴옥시-메틸-(2,4,6,-트라이아이소프로필페닐)실란; 및 (1-메틸-2-프로핀-1-일)옥시다이페닐실란으로 이루어진 군으로부터 선택될 수 있다.

(1-methyl-2-propin-1-yl)oxydiphenylsilane. Alternatively, the starting material c) is a hydrocarbyloxy-functional arylsilane such as (1,1-dimethyl-2-propenyl)oxydiphenylsilane; (1-methyl-2-propenyl)oxydiphenylsilane; allyloxy-diphenylsilane; allyloxy-bis(2,4,6-trimethylphenyl)silane; allyloxy-methyl-(2,4,6-tri-isopropylphenyl)silane; and/or (1-methyl-2-propin-1-yl)oxydiphenylsilane. Alternatively, starting material c), the accelerator is allyloxy-bis(2,4,6-trimethylphenyl)silane; allyloxy-methyl-(2,4,6,-triisopropylphenyl)silane; and (1-methyl-2-propin-1-yl)oxydiphenylsilane.

Suitable accelerators of some of the above formulas and methods for their preparation are known, for example, from Japanese Patent Laid-Open Nos. 11209384 (A) and 2002255975 (A). Alternatively, accelerators for use in the methods herein may be prepared by combining starting materials comprising, for example, an allyl-functional alcohol and an allyl-functional amine to form a mixture, and converting the mixture into a SiH- It may be synthesized by a method comprising the step of adding to a functional halosilane, which may optionally be carried out in the presence of a solvent (eg, those described herein as starting material e). The resulting reaction product can be purified, for example, by filtration, stripping and/or distillation to recover the accelerator. Alternatively, accelerators for use in the methods herein may be synthesized, for example, by the methods of Reference Examples 1 and 2 described below.

Alternatively, accelerators such as the hydrocarbyloxy-functional arylsilanes described above can be synthesized by, for example, a method comprising:

One)

a) an unsaturated alcohol, and

b) combining starting materials comprising an amine,

c) forming a mixture, and

2) c) adding the mixture to d) the SiH-functional halosilane to form a f) reaction product comprising g) a promoter. The process may optionally be carried out in the presence of e) a solvent. Steps 1) and 2) can be carried out at room temperature; Alternatively, steps 1) and 2) may be performed at -20°C to 40°C; Alternatively, it may be carried out at a temperature of 0°C to 20°C.

The method described above may optionally further comprise step 3) f) recovering g) promoter from the reaction mixture. The recovery in step 3) may be effected by any convenient means, for example by filtration, washing with a solvent, stripping and/or distillation, such that unreacted starting material, by-products, if present, and e) if used g) accelerator can be recovered from the solvent. One or more of these method steps may be performed under an inert atmosphere, such as nitrogen. For example, steps 1) and 2) described above may optionally further comprise flowing an inert gas through the vessel headspace. Without wishing to be bound by theory, it is believed that flowing an inert gas through the reactor headspace may help remove low boiling point impurities from the system.

Starting material a) unsaturated alcohol

을 가질 수 있으며, 여기서 R¹, R², R³, R⁴ 및 하첨자 a 및 b는 상기에 기재된 바와 같다. 적합한 불포화 알코올은 당업계에 공지되어 있으며 구매가능하다. 예를 들어, 알릴 알코올 및 프로파르길 알코올은 미국 미주리주 세인트 루이스 소재의 밀리포어 시그마로부터 입수가능하다. 알코올은 출발 재료 d) SiH-작용성 할로실란에 대해 1:1 비로 사용될 수 있으며; 대안적으로, 1.1 알코올 대 1 할로실란으로 사용될 수 있다. 특히 수소 가스 생성이 서서히 발생할 수 있는 프로파르길 알코올, HC≡C-CH₂-OH의 경우, -OH가 Si-H와 반응하여 수소를 생성할 수 있으므로, 너무 많은 알코올을 사용하는 것을 피하는 것이 중요하다. 할라이드 불순물이 촉매의 선택성을 감소시키기 때문에, 잔류 할로실란을 최소화하는 것이 또한 중요하다. 알코올이 비극성 유기 용매에서 암모늄 염의 용해도를 증가시켜 여과에 의한 암모늄 할라이드 염의 제거가 덜 효과적이게 되도록 당업계에 공지되어 있으므로, 최소의 과잉 알코올을 갖는 것이 또한 중요하다.The unsaturated alcohol used to prepare the accelerator has the formula

wherein R ¹ , R ² , R ³ , R ⁴ and the subscripts a and b are as described above. Suitable unsaturated alcohols are known in the art and are commercially available. For example, allyl alcohol and propargyl alcohol are available from Millipore Sigma, St. Louis, MO. Alcohols may be used in a 1:1 ratio to the starting material d) SiH-functional halosilanes; Alternatively, 1.1 alcohol to 1 halosilane may be used. In particular, in the case of propargyl alcohol, HC≡C-CH ₂ -OH, where hydrogen gas generation can occur slowly, -OH can react with Si-H to produce hydrogen, so it is better to avoid using too much alcohol. It is important. It is also important to minimize residual halosilanes, as halide impurities reduce the selectivity of the catalyst. It is also important to have a minimum excess of alcohol, as alcohols are known in the art to increase the solubility of ammonium salts in non-polar organic solvents, making removal of ammonium halide salts by filtration less effective.

starting material b) amine

The starting material b) in this process for preparing the accelerator may be a tertiary amine. The tertiary amine may be a trialkyl amine. The trialkyl amine may have the formula NR ²¹ ₃ , wherein each R ²¹ is from 2 to 16 carbon atoms, alternatively from 2 to 12 carbon atoms, alternatively from 2 to 8 carbon atoms, alternatively 2 an independently selected alkyl group of to 4 carbon atoms. Alternatively, the trialkyl amine may be triethylamine. Tertiary amines are known in the art and are commercially available, for example, from Millipore Sigma, St. Louis, MO. Alternatively, the starting material b) may comprise pyridine and derivatives thereof. The starting material b) may be used in a 1:1 molar ratio to the starting material d), the SiH-functional halosilane, alternatively, the amounts of the starting material b) and the starting material d) in a b):d) ratio of 1.5: One; Alternatively, it may be 1:1 to 1.1:1. Without wishing to be bound by theory, it is believed that it is important to have a sufficient amount of starting material b) (eg trialkyl amines) to d) maximize consumption of halides of SiH-functional halosilanes. Without wishing to be bound by theory, it is desirable to have a minimal excess of starting material b) (e.g. trialkyl amines) to increase the solubility of the ammonium salt in a non-polar organic solvent so that removal of the ammonium halide salt by filtration becomes less effective. It is also considered important.

Starting material d) SiH-functional halosilanes

을 가질 수 있으며, 여기서 R⁵ 및 R⁶은 상기에 기재된 바와 같고, X는 F, Cl, Br 및 I로 이루어진 군으로부터 선택되는 할로겐 원자이고; 대안적으로 F, Cl 및 Br이고; 대안적으로 Cl 및 Br이고; 대안적으로 Cl이고; 대안적으로 Br이다. 적합한 SiH-작용성 할로실란의 예에는 다이페닐클로로실란(Ph₂HSiCl), 페닐메틸클로로실란(PhMeHSiCl), 클로로-메틸-(2,4,6-트라이아이소프로필페닐)실란, 및 클로로-다이-(2,4,6-트라이메틸페닐)실란이 포함된다. 적합한 SiH-작용성 할로실란은 구매가능하다. 예를 들어, 다이페닐클로로실란은 미국 미주리주 세인트 루이스 소재의 밀리포어 시그마로부터 입수가능하다. 대안적으로, SiH-작용성 할로실란은 공지된 방법, 예컨대 에테르 및 선택적으로 출발 재료 e)에 대해 본 명세서에 기재된 바와 같은 용매의 존재 하에 하이드리도할로실란(예를 들어, 화학식 H_dR²² _eSiX_(4-d-e)의 것, 여기서 X는 상기에 기재된 바와 같고; R²²는 1 내지 18개의 탄소 원자, 대안적으로 1 내지 12개의 탄소 원자, 대안적으로 1 내지 6개의 탄소 원자의 알킬 기, 대안적으로 메틸이고; 하첨자 d는 1 또는 2이고, 하첨자 e는 0 또는 1이고, 수량 (d + e) < 4임)과 아릴 그리냐르(Grignard) 시약, 예컨대 아릴마그네슘 브로마이드의 그리냐르 반응에 의해 합성될 수 있다. 당업자는 미국 특허 제7,456,308호 및 미국 특허 제7,351,847호 및 그 안에 인용된 참고문헌에 개시된 바와 같은 방법을 사용하여 적절한 출발 재료를 변화시킴으로써 상기에 기재된 SiH-작용성 할로실란을 제조할 수 있을 것이다.The starting material d) in this process for preparing the accelerator is a SiH-functional halosilane. SiH-functional halosilanes have the formula

wherein R ⁵ and R ⁶ are as described above, and X is a halogen atom selected from the group consisting of F, Cl, Br and I; alternatively F, Cl and Br; alternatively Cl and Br; alternatively Cl; alternatively Br. Examples of suitable SiH-functional halosilanes include diphenylchlorosilane (Ph ₂ HSiCl), phenylmethylchlorosilane (PhMeHSiCl), chloro-methyl-(2,4,6-triisopropylphenyl)silane, and chloro-di -(2,4,6-trimethylphenyl)silane. Suitable SiH-functional halosilanes are commercially available. For example, diphenylchlorosilane is available from Millipore Sigma, St. Louis, MO. Alternatively, SiH-functional halosilanes can be prepared using known methods such as hydridohalosilanes (eg, formula H _d R ) in the presence of a solvent as described herein for ether and optionally starting material e) ²² _e of SiX _(4-de) , wherein X is as described above; R ²² is of 1 to 18 carbon atoms, alternatively 1 to 12 carbon atoms, alternatively 1 to 6 carbon atoms an alkyl group, alternatively methyl; the subscript d is 1 or 2, the subscript e is 0 or 1, and the quantity (d + e) < 4) and an aryl Grignard reagent such as arylmagnesium bromide It can be synthesized by the Grignard reaction of One skilled in the art will be able to prepare the SiH-functional halosilanes described above by varying the appropriate starting materials using methods as disclosed in US Pat. No. 7,456,308 and US Pat. No. 7,351,847 and references cited therein.

starting material e) solvent

The starting material e) in this process for preparing the accelerator is a solvent which may optionally be added during and/or after step 1) and/or step 2) of this process. Suitable solvents include polyalkylsiloxanes, aromatic hydrocarbons, aliphatic hydrocarbons, mineral spirits, naphtha, or combinations thereof. Polyalkylsiloxanes having suitable vapor pressures may be used as solvents, including hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane and other low molecular weight polyalkylsiloxanes such as Dow Silicones Corporation, Midland, Michigan, USA. 0.5 to 1.5 cSt DOWSIL™ 200 Fluids and DOWSIL™ OS Fluids commercially available from

Alternatively, the starting material e) may comprise an organic solvent. Organic solvents include aromatic hydrocarbons such as benzene, toluene or xylene; aliphatic hydrocarbons such as pentane, heptane, hexane or octane; mineral spirits; naphtha; or a combination thereof.

The amount of solvent will depend on a variety of factors including the type of solvent selected for the methods described herein and the amounts and types of other starting materials. However, the amount of solvent may be 0% to 95% based on the total weight of starting material a), starting material b), starting material c), starting material d) and starting material e). A solvent may be added during step 1) and/or step 2) to aid, for example, in mixing and transferring one or more starting materials. The method may optionally further comprise removing all or part of the solvent after step 2).

Alternatively, the accelerators described above are, for example, compounds of the formula MO-CH ₂ -CH=CH ₂ , wherein M is selected from the group consisting of Li, Na, K, Rb and Cs, as starting material a). can be synthesized by a method comprising the step of using the starting material d) in a 1:1 ratio with the SiH-functional halosilane described above. Alternatively, the hydrocarbyloxy-functional arylsilanes described above have, for example, the formula M'-(O-CH ₂ -CH=CH ₂ ) ₂ , wherein M' gives the corresponding metal halide salt. = Mg, Ca, Sr, Ba) as the starting material a).

Accelerator is 1:3 or greater; alternatively 1:5 or more; Alternatively used in an amount sufficient to provide a platinum to accelerator ratio of at least 1:8. However, the amount of promoter in the reaction mixture should be less than 5% of the total mass of reagents, catalysts, solvents and promoters. Examples of accelerators (and abbreviations for accelerators to be discussed in the Examples) are provided in Table 1 below.

[Table 1]

Starting material d) SiH-terminated siloxane oligomers

을 가질 수 있고, 여기서 각각의 R⁸은 1 내지 18개의 탄소 원자의 독립적으로 선택된 1가 탄화수소 기이고, 하첨자 x는 1 또는 2이다. 각각의 R⁸은 알킬 기 또는 아릴 기일 수 있다. R⁸에 적합한 알킬 기는 R⁹에 대해 상기에 기재된 것들로 예시된다. R⁸에 적합한 아릴 기는 사이클로펜타다이에닐, 페닐, 톨릴, 자일릴, 안트라세닐, 벤질, 1-페닐에틸, 2-페닐에틸 및 나프틸로 예시된다. 단환식 아릴 기는 5 내지 9개의 탄소 원자, 대안적으로 6 또는 7개의 탄소 원자, 대안적으로 5 또는 6개의 탄소 원자를 가질 수 있다. 다환식 아릴 기는 10 내지 17개의 탄소 원자, 대안적으로 10 내지 14개의 탄소 원자, 대안적으로 12 내지 14개의 탄소 원자를 가질 수 있다. 대안적으로, R⁸에 대한 아릴 기는 페닐일 수 있다. 대안적으로, 각각의 R⁸은 알킬 기, 대안적으로 메틸일 수 있다. 대안적으로, SiH-말단화된 실록산 올리고머는 1,1,3,3-테트라메틸다이실록산 및 1,1,3,3,5,5-헥사메틸트라이실록산으로 이루어진 군으로부터 선택될 수 있고, 이들은 각각 미국 미시간주 미들랜드 소재의 다우 실리콘즈 코포레이션 및 미국 펜실베이니아주 모리스빌 소재의 젤레스트, 인크.(Gelest, Inc.)로부터 입수가능하다. 출발 재료 a) 및 출발 재료 d)의 양은 알릴-작용성 아민 대 올리고머 비가 5:1 내지 1:2, 대안적으로 2:1 내지 1:1.2, 대안적으로 1.2:1 내지 1:1.1의 범위일 수 있는 것이다.In the process for preparing cyclic polysiloxazanes, the starting material d) is a SiH-terminated siloxane oligomer. The oligomer has the chemical formula

wherein each R ⁸ is an independently selected monovalent hydrocarbon group of 1 to 18 carbon atoms and the subscript x is 1 or 2. Each R ⁸ may be an alkyl group or an aryl group. Suitable alkyl groups for R ⁸ are exemplified by those described above for R ⁹ . Suitable aryl groups for R ⁸ are exemplified by cyclopentadienyl, phenyl, tolyl, xylyl, anthracenyl, benzyl, 1-phenylethyl, 2-phenylethyl and naphthyl. A monocyclic aryl group may have 5 to 9 carbon atoms, alternatively 6 or 7 carbon atoms, alternatively 5 or 6 carbon atoms. A polycyclic aryl group may have from 10 to 17 carbon atoms, alternatively from 10 to 14 carbon atoms, alternatively from 12 to 14 carbon atoms. Alternatively, the aryl group for R ⁸ can be phenyl. Alternatively, each R ⁸ can be an alkyl group, alternatively methyl. Alternatively, the SiH-terminated siloxane oligomer may be selected from the group consisting of 1,1,3,3-tetramethyldisiloxane and 1,1,3,3,5,5-hexamethyltrisiloxane, They are available from Dow Silicons Corporation of Midland, Michigan and Gelest, Inc. of Morrisville, PA, respectively. The amounts of starting material a) and starting material d) range in an allyl-functional amine to oligomer ratio from 5:1 to 1:2, alternatively from 2:1 to 1:1.2, alternatively from 1.2:1 to 1:1.1. it could be

starting material e) solvent

The starting material e) in the process for preparing the cyclic polysiloxazane is a solvent which may optionally be added during and/or after step 1) of this process. Suitable solvents include polyalkylsiloxanes, aromatic hydrocarbons, aliphatic hydrocarbons, glycol dialkyl ethers, dialkyl ethers, alkyl-polyglycol ethers, cyclic alkyl ethers, tetrahydrofuran, mineral spirits, naphtha, or combinations thereof. Polyalkylsiloxanes having suitable vapor pressures may be used as solvents, including hexamethyldisiloxane, octamethyltrisiloxane and other low molecular weight polyalkylsiloxanes such as 0.5 to 1.5 commercially available from Dow Silicones Corporation, Midland, Michigan. cSt Dousil™ 200 Fluid and Dousil™ OS Fluid.

Alternatively, the starting material e) may comprise an organic solvent. Organic solvents include aromatic hydrocarbons such as benzene, toluene or xylene; aliphatic hydrocarbons such as heptane, hexane, or octane; tetraglyme, or ethylene glycol n-butyl ether, di-n-butyl ether, tetrahydrofuran; mineral spirits; naphtha; or a combination thereof.

The amount of solvent will depend on a variety of factors including the type of solvent selected for use in the methods described above and the amounts and types of other starting materials. However, the amount of solvent may be 0% to 50%, based on the total weight of starting material a), starting material b), starting material c), starting material d) and starting material e). A solvent may be added during step 1) and/or step 2) to aid, for example, in mixing and transferring one or more starting materials. For example, the catalyst may be delivered in a solvent. The method may optionally further comprise removing all or part of the solvent after step 2).

Additional details on this method step

Step 1) of the process described herein comprises, as described above, a) an allyl-functional amine, b) a platinum catalyst capable of catalyzing the hydrosilylation reaction, c) a hydrosilylation reaction promoter, and optionally e) combining the starting materials comprising a solvent. The combination in step 1) comprises mixing starting material a), starting material b) and starting material c) to form a reaction mixture, wherein the reaction mixture is heated to 150° C. or lower, alternatively 120° C. or lower, alternatively 110° C. Hereinafter, alternatively, heating to a temperature of 95° C. or less, alternatively 50° C. to 150° C. may be carried out.

Alternatively, the starting material b), the platinum catalyst and the starting material c), the hydrosilylation reaction promoter may be combined before combining the starting material a), the allyl-functional amine in step 1). For example, starting material b) and starting material c) are at least one day, alternatively at least one week, alternatively at least two weeks, alternatively one month, alternatively before combining with starting material a) in step 1). typically at least 4 hours, alternatively 4 hours to 4 months under ambient conditions (room temperature and ambient pressure), optionally by mixing in the presence of a solvent. If the starting material c) contains a carbon-carbon triple bond, after combining it with the starting material b) a platinum catalyst, the resulting mixture is mixed with the starting material a) allyl-functional amine or starting material d) SiH-terminated in combination with any of the siloxane oligomers. The mixture prepared by combining starting material b) with starting material c) may be aged at room temperature for at least 1 week, alternatively for 2 weeks, alternatively for 1 month before combining with starting material a) or starting material d). have. Alternatively, when the starting material b) and the starting material c) are mixed at an elevated temperature, for example, above 30° C. to 90° C., the aging time can be reduced.

In step 2) of the process for preparing the cyclic polysiloxazane, step 2) is 20° C. to 200° C., alternatively 50° C. to 150° C., alternatively 70° C. to 110° C., alternatively 70° C. to more than 110° C. can be carried out at a temperature of Without wishing to be bound by theory, it is believed that d) adding the Si-terminated siloxane oligomer incrementally or slowly over time may improve the safety of the methods described herein. By controlling the temperature and addition of reactants, the potential for uncontrolled exothermic reactions can be minimized.

The method may further comprise step 3) of optionally purifying the cyclic polysiloxazane after step 2). For example, the process described above can produce a crude product comprising a cyclic polysiloxazane, unreacted starting material, and, if used, a solvent. Step 3) can optionally be carried out by stripping and/or distillation under vacuum, for example by heating to 120° C.

Cyclic siloxazan

(하첨자 x = 0인 경우) 및

(하첨자 x = 1인 경우)로 이루어진 군으로부터 선택되는 일반 화학식을 가지며, 여기서 R⁸ 및 R⁹는 상기에 기재된 바와 같다.The method described above produces cyclic siloxazanes. Cyclic siloxazan is

(if subscript x = 0) and

It has a general formula selected from the group consisting of (when subscript x = 1), wherein R ⁸ and R ⁹ are as described above.

을 갖고, 이는 -SiMe₂OSiMe₂C₃H₆NH-(즉, 1,1,3,3-테트라메틸-2-옥사-7-아자-1,3-다이실라사이클로헵탄)으로 축약될 수 있으며; SiH-말단화된 실록산 올리고머가 1,1,3,3,5,5-헥사메틸트라이실록산이고 알릴-작용성 아민이 알릴 아민(각각의 R⁸은 메틸이고 각각의 R⁹는 수소임)인 경우, 환형 폴리실록사잔은 화학식

을 갖고, 이는 -SiMe₂OSiMe₂OSiMe₂C₃H₆NH-(즉, 1,1,3,3,5,5-헥사메틸-2,4-다이-옥사-9-아자-1,3,5-트라이실라사이클로노난)으로 축약될 수 있다.For example, the SiH-terminated siloxane oligomer is 1,1,3,3-tetramethyldisiloxane and the allyl-functional amine is allyl amine (each R ⁸ is methyl and each R ⁹ is hydrogen) When , the cyclic polysiloxazane is represented by the formula

, which can be abbreviated as -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- (ie, 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane). there is; wherein the SiH-terminated siloxane oligomer is 1,1,3,3,5,5-hexamethyltrisiloxane and the allyl-functional amine is allyl amine (each R ⁸ is methyl and each R ⁹ is hydrogen) If, the cyclic polysiloxazane is of the formula

has -SiMe ₂ OSiMe ₂ OSiMe ₂ C ₃ H ₆ NH- (ie, 1,1,3,3,5,5-hexamethyl-2,4-di-oxa-9-aza-1,3 ,5-trisilacyclononane).

Alternatively, when the SiH-terminated siloxane oligomer is 1,1,3,3-tetramethyldisiloxane and the allyl-functional amine is N-allyl-N,N-dimethylamine, the cyclic polysiloxazane has the formula

을 갖고; SiH-말단화된 실록산 올리고머가 1,1,3,3,5,5-헥사메틸트라이실록산이고 알릴-작용성 아민이 N-알릴-N,N-다이메틸아민인 경우, 환형 폴리실록사잔은 화학식

을 갖는다.

have; When the SiH-terminated siloxane oligomer is 1,1,3,3,5,5-hexamethyltrisiloxane and the allyl-functional amine is N-allyl-N,N-dimethylamine, the cyclic polysiloxazane has the formula

has

Alternatively, when the SiH-terminated siloxane oligomer is 1,1,3,3-tetramethyldisiloxane and the allyl-functional amine is 2-methyl-allylamine, the cyclic polysiloxazane has the formula

을 갖고, 이는 -SiMe₂OSiMe₂CH₂CH(CH₃)CH₂NH-(즉, 1,1,3,3,5-펜타메틸-2-옥사-7-아자-1,3,5-다이실라사이클로헵탄)로 축약될 수 있다. 그리고, SiH-말단화된 실록산 올리고머가 1,1,3,3,5,5-헥사메틸트라이실록산이고 알릴-작용성 아민이 2-메틸-알릴아민인 경우, 환형 폴리실록사잔은 화학식

, 즉, 1,1,3,3,5,5,7-헵타메틸-2,3-다이-옥사-9-아자-1,3,5-트라이실라사이클로노난을 갖는다. 상기에 기재된 방법에 의해 제조된 환형 폴리실록사잔은 아미노-작용성 폴리오르가노실록산을 제조하는 데 유용하다.

has -SiMe ₂ OSiMe ₂ CH ₂ CH(CH ₃ )CH ₂ NH- (ie, 1,1,3,3,5-pentamethyl-2-oxa-7-aza-1,3,5- disilacycloheptane). And, when the SiH-terminated siloxane oligomer is 1,1,3,3,5,5-hexamethyltrisiloxane and the allyl-functional amine is 2-methyl-allylamine, the cyclic polysiloxazane has the formula

, that is, 1,1,3,3,5,5,7-heptamethyl-2,3-di-oxa-9-aza-1,3,5-trisilacyclononane. Cyclic polysiloxazanes prepared by the methods described above are useful for preparing amino-functional polyorganosiloxanes.

Without wishing to be bound by theory, it is believed that the methods described herein are capable of producing cyclic polysiloxazanes with advantageous purity profiles. For example, the cyclic polysiloxazane may have a SiH content < 100 ppm, an unsaturated olefin content < 100 ppm and/or an allyl-functional amine content < 50 ppm, wherein the content is GC Can be measured by -FID, GC-mass spectrometry, ¹ H NMR, ¹³ C NMR and ²⁹ Si NMR (impurities cannot be detected with a conservative instrument Limit of Detection of 50 ppm). Moreover, this purity profile is believed to be advantageous for forming amino-functional polyorganosiloxanes suitable for use in personal care applications. Allyl-functional amines and SiH containing ingredients are generally undesirable in personal care compositions, such as hair care compositions. Accordingly, the cyclic polysiloxazanes described above are useful for capping silanol-functional polyorganosiloxanes, such as silanol terminated polydimethylsiloxanes, thereby making them suitable for use in personal care compositions amino-functional Polyorganosiloxanes can be prepared. Moreover, the present inventors surprisingly found that during the synthesis of cyclic -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH-, a new intermediate is formed. The intermediate has the formula H ₂ N(C ₃ H ₆ )SiMe ₂ OSiMe ₂ NH—CH ₂ CH=CH ₂ .

Part II. Preparation of amino-functional polyorganosiloxanes

A. Process for preparing amino-functional polyorganosiloxanes using cyclic polysiloxazanes

A method for preparing an amino-functional organosilicon compound (eg, an amino-functional silane and/or an amino-functional polyorganosiloxane) comprises:

One)

A) a cyclic polysiloxazane prepared as described above, and

D) D-I) a silanol-functional silane, D-II) a silanol-functional polyorganosiloxane, or a silanol-functional organosilicon which may be selected from the group consisting of both D-I) and D-II) combining starting materials comprising the compound to prepare a reaction product comprising an amino-functional organosilicon compound; and

optionally 2) recovering the amino-functional organosilicon compound.

Starting material D-I) Silanol-functional silanes

The silanol-functional silane may have the formula HOSiR ²¹ R ²² R ²³ , wherein R ²¹ , R ²² and R ²³ are each independently selected from 1 to 18 carbons as described and exemplified above for R ⁸ . It is a monovalent hydrocarbon group of atoms. Alternatively, R ²¹ , R ²² and R ²³ can each independently be an alkyl group of 1 to 15 carbon atoms, alternatively 1 to 12 carbon atoms, alternatively 1 to 6 carbon atoms. Alternatively, R ²¹ , R ²² and R ²³ are each independently methyl, ethyl, propyl (eg iso-propyl and/or n-propyl), butyl (eg isobutyl, n-butyl, tert-butyl and/or sec-butyl), pentyl (eg isopentyl, neopentyl and/or tert-pentyl), hexyl, heptyl, octyl, nonyl and decyl, as well as cycloalkyls such as cyclopentyl and cyclohexyl. branched saturated monovalent hydrocarbyl group of 6 or more carbon atoms comprising the group. Alternatively, each alkyl group for R ²¹ , R ²² and R ²³ is methyl, ethyl, propyl or butyl; Alternatively it may be ethyl or propyl. Silanol-functional silanes are known in the art and are commercially available. For example, triethylsilanol and triisopropylsilanol are commercially available from Millipore Sigma, St. Louis, MO.

Starting material D-II) Silanol-functional polyorganosiloxane

The starting material D-II) in the process for preparing the amino-functional polyorganosiloxane comprises a silanol-functional polyorganosiloxane. Silanol-functional polyorganosiloxanes have at least one silicon-bonded hydroxyl (silanol) group per molecule. The silanol-functional polyorganosiloxane may be linear, branched, partially branched, cyclic, resinous (ie, having a three-dimensional network), or may comprise a combination of different structures. For example, the silanol-functional polyorganosiloxane may contain any of M, D, T and/or Q units, as long as the silanol-functional polyorganosiloxane comprises at least one silicon-bonded hydroxyl group. may include a combination of These siloxy units can be combined in various ways to form cyclic, linear, branched and/or dendritic (three-dimensional networked) structures. Alternatively, the silanol-functional polyorganosiloxane may be a silanol-functional polydiorganosiloxane. The silanol-functional polyorganosiloxane may have silanol groups at terminal positions, pendant positions, or both terminal and pendant positions.

Silanol groups may be present in any M, D and/or T units present in the silanol-functional polyorganosiloxane and may be bonded to the same silicon atom (for M and/or D siloxy units). . Silanol-functional polyorganosiloxanes are, for example, as M units (R ⁸ ₃ SiO _1/2 ), (R ⁸ ₂ (OH)SiO _1/2 ), (R ⁸ (OH) ₂ SiO _{1/ 2} ) and/or ((OH) ₃ SiO _1/2 ), wherein R ⁸ is as described above. Silanol-functional polyorganosiloxanes are, for example, as D units (R ⁸ ₂ SiO _2/2 ), (R ⁸ (OH)SiO _2/2 ) and/or ((OH) ₂ SiO _2/2 ) ) may be included. The silanol-functional polyorganosiloxane may, for example, comprise (R ⁸ SiO _3/2 ) and/or ((OH)SiO _3/2 ) as T units. Such siloxy units may be combined in any manner, optionally with Q units, to provide a silanol-functional polyorganosiloxane having at least one silicon-bonded OH group per molecule.

The silanol-functional polyorganosiloxane is branched or dendritic when D-II) the silanol-functional polyorganosiloxane comprises T units and/or Q units. When the silanol-functional polyorganosiloxane is branched or dendritic, the silanol-functional polyorganosiloxane is typically a copolymer comprising M units and/or D units together with T units and/or Q units. to be. For example, the silanol-functional polyorganosiloxane can be a DT resin, MT resin, MDT resin, DTQ resin, MTQ resin, MDTQ resin, DQ resin, MQ resin, DTQ resin, MTQ resin, or MDQ resin. Alternatively, the silanol-functional polyorganosiloxane may be linear, in which case the silanol-functional polyorganosiloxane is a silanol-functional polydiorganosiloxane comprising D units together with M units. to be.

The silanol-functional polyorganosiloxane for the starting material D-II) may be a silanol-functional polydiorganosiloxane. Silanol-functional polydiorganosiloxane is of unit formula (D1): (R ⁸ ₃ SiO _1/2 ) _e (R ⁸ ₂ SiO _2/2 ) _f (R ⁸ (OH)SiO _2/2 ) _g ( R ⁸ ₂ (OH)SiO _1/2 ) _h , wherein R ⁸ is as described above, the subscripts are 2 ≥ e ≥ 0, 4000 ≥ f ≥ 0, 4000 ≥ g ≥ 0, and 2 ≥ h ≥ 0, provided that quantity (e + h) = 2, quantity (g + h) ≥ 2, and quantity 4 ≤ (e + f + g + h) ≤ 8000. Alternatively, 4 ≤ (e + f + g + h) ≤ 4000. Alternatively, 10 ≤ (e + f + g + h) ≤ 2000. Alternatively, the subscripts e through h have a viscosity measured at 25° C. from 8 mPa·s to 100,000,000 mPa·s; alternatively from 8 mPa·s to 40,000,000 mPa·s, from 70 mPa·s to less than 1,000,000 mPa·s, alternatively from 70 mPa·s to 500,000 mPa·s, alternatively from 10 mPa·s to 150,000 mPa·s, Alternatively, it may have a value sufficient to provide a silanol-functional polydiorganosiloxane that is between 70 mPa·s and 16,000 mPa·s. Alternatively, each R ⁸ may be selected from alkyl and aryl. Alternatively, each R ⁸ may be selected from methyl and phenyl. Alternatively, at least 80% of all R ⁸ groups are methyl.

Alternatively, the silanol-functional polydiorganosiloxane may be a silanol-terminated polydiorganosiloxane. The silanol-terminated polydiorganosiloxane may have the formula (D2):

, 상기 식에서, R¹¹은 OH 및 R⁸로 이루어진 군으로부터 선택되고, 하첨자 y는 25℃에서 측정되는 점도가 8 mPa·s 내지 100,000,000 mPa·s; 대안적으로 8 mPa·s 내지 40,000,000 mPa·s, 70 mPa·s 내지 1,000,000 mPa·s 미만, 대안적으로 70 mPa·s 내지 500,000 mPa·s; 대안적으로 70 mPa·s 내지 500,000 mPa·s, 대안적으로 10 mPa·s 내지 150,000 mPa·s, 대안적으로 70 mPa·s 내지 16,000 mPa·s인 실란올-작용성 폴리다이오르가노실록산을 제공하기에 충분한 값을 갖는다(대안적으로, y는 2 내지 4000일 수 있고; 대안적으로 y는 2 내지 2000일 수 있다). 출발 재료 A)로서 사용하기에 적합한 실란올-말단화된 폴리다이오르가노실록산은 당업계에 공지된 방법, 예컨대 상응하는 유기할로실란의 가수분해 및 축합 또는 환형 폴리다이오르가노실록산의 평형화에 의해 제조될 수 있다.

, wherein R ¹¹ is selected from the group consisting of OH and R ⁸ , and the subscript y has a viscosity measured at 25° C. of 8 mPa·s to 100,000,000 mPa·s; alternatively between 8 mPa·s and 40,000,000 mPa·s, between 70 mPa·s and less than 1,000,000 mPa·s, alternatively between 70 mPa·s and 500,000 mPa·s; alternatively from 70 mPa·s to 500,000 mPa·s, alternatively from 10 mPa·s to 150,000 mPa·s, alternatively from 70 mPa·s to 16,000 mPa·s; (alternatively, y may be 2 to 4000; alternatively, y may be 2 to 2000). Silanol-terminated polydiorganosiloxanes suitable for use as starting material A) are prepared by methods known in the art, such as hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic polydiorganosiloxanes. can be manufactured by

Alternatively, the silanol-functional polyorganosiloxane may be a silanol-functional polysiloxane resin. The polysiloxane resin may have the unit formula (D3): (R ²⁰ ₃ SiO _1/2 ) _A (R ²⁰ ₂ SiO _2/2 ) _B (R ²⁰ SiO _3/2 ) _C (SiO _4/2 ) _D , where subscript A, subscript B, subscript C and subscript D are mole fractions having a value such that 0 ≤ A ≤ 0.6, 0 ≤ B ≤ 0.5, 0 ≤ C ≤ 1, 0 ≤ D ≤ 1. , the singular quantity (C + D) > 0. In the polysiloxane resin, each R ²⁰ is independently a monovalent hydrocarbon group or a hydrolysable group (eg, a hydroxyl group or an alkoxy group) as described above for R ⁸ . At least one R ²⁰ per molecule is a hydrolysable group. Suitable hydrolysable groups include hydroxyl; alkoxy such as methoxy and ethoxy; alkyloxy such as isopropenyloxy; amidoxy, such as acetamidoxy; and aminooxy, such as N,N-dimethylaminoxy.

Alternatively, the polysiloxane resin may be (D4) a polyorganosilicate resin or (D5) a silsesquioxane resin. The polyorganosilicate resin comprises monofunctional units of formula R ²⁰ ₃ SiO _1/2 (M units) and tetrafunctional silicate units of formula SiO _4/2 (Q units), wherein R ²⁰ is as described above like a bar Alternatively, in the polyorganosilicate resin, the monovalent hydrocarbon group for R ²⁰ can be independently selected from the group consisting of alkyl, alkenyl and aryl, such as those described above for R ⁸ . Alternatively, the monovalent hydrocarbon group for R ²⁰ may be selected from alkyl and aryl. Alternatively, the monovalent hydrocarbon group for R ²⁰ may be selected from methyl and phenyl. Alternatively, at least 1/3, alternatively at least 2/3 of the R ²⁰ groups are methyl groups. Alternatively, M units in polyorganosilicate resins can be exemplified by (Me ₃ SiO _1/2 ) and (Me ₂ PhSiO _1/2 ). Polyorganosilicate resins are liquid hydrocarbons, such as solvents exemplified by benzene, toluene, xylene and heptane, or liquid organosilicon compounds such as low-viscosity linear and cyclic polydiorganosiloxanes (eg, methods for preparing cyclic polysiloxazanes). is soluble in the solvent) described above for the starting material e) in

When prepared, the polyorganosilicate resin comprises the aforementioned M units and Q units, and the polyorganosiloxane further comprises units having silicon-bonded hydroxyl groups and is a neopenta of the formula Si(OSiR ²⁰ ₃ ) ₄ a neopentamer, wherein R ²⁰ is as described above, for example the neopentamer may be tetrakis(trimethylsiloxy)silane. ²⁹ Si NMR spectroscopy (as described below) can be used to determine the hydroxyl content, and the molar ratio of M and Q units, wherein the ratio is {M ( resin)}/{Q(resin)}. The M:Q ratio represents the molar ratio of the total number of triorganosiloxy groups (M units) in the dendritic portion of the polyorganosilicate resin to the total number of silicate groups (Q units) in the dendritic portion. The M:Q ratio may be from 0.5:1 to 1.5:1, alternatively from 0.6:1 to 0.9:1.

The MQ silicone resin may contain up to 5.0%, alternatively up to 0.7%, alternatively up to 0.3% of the terminal units represented by the formula X"SiO _3/2 , wherein X" is a hydrolysable group, such as a hydride loxyl; alkoxy such as methoxy and ethoxy; alkenyloxy such as isopropenyloxy; amidoxy, such as acetamidoxy; and aminooxy, such as N,N-dimethylaminoxy. The concentration of silanol groups present in the silicone resin can be determined using ¹ H NMR and/or ²⁹ Si NMR.

The Mn for achieving the desired flow characteristics of the MQ silicone resin may depend, at least in part, on the Mn of the silicone resin and the type of hydrocarbon groups represented by R ²⁰ present in this starting material. The Mn of the MQ silicone resin is typically greater than 1,000 Da, alternatively from 1,000 Da to 15,000 Da, alternatively from greater than 3,000 Da to 8,000 Da, alternatively from 4,500 Da to 7,500 Da.

The MQ silicone resin may be prepared by any suitable method. Reportedly, silicone resins of this type have been prepared by cohydrolysis of the corresponding silanes, or by silica hydrosol capping methods known in the art. Briefly, the method comprises reacting a silica hydrosol under acidic conditions with a hydrolysable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or a combination thereof, and M and Q units. and recovering the product (MQ resin). The resulting MQ resin may contain from 2 to 5% by weight of silicon-bonded hydroxyl groups.

The intermediate used to prepare the polyorganosilicate resin may be a triorganosilane, and a silane or alkali metal silicate having four hydrolysable substituents. The triorganosilane may have the formula R ⁸ ₃ SiX ¹ , wherein R ⁸ is as described above and X ¹ represents a hydrolysable substituent as described above for X″. The silane having may have the formula SiX ² ₄ , wherein each X ² is halogen, alkoxy or hydroxyl Suitable alkali metal silicates include sodium silicate.

Polyorganosilicate resins prepared as described above have silicon-bonded hydroxyl groups, namely formula HOSi _3/2 , (HO) ₂ Si _2/2 , (HO) ₃ Si _1/2 and/or HOR ²⁰ _{2 .} It typically contains groups of SiO _1/2 . The polyorganosilicate resin may comprise up to 5% silicon-bonded hydroxyl groups as determined by FTIR spectroscopy. For certain applications, it may be desirable for the amount of silicon-bonded hydroxyl groups to be less than 0.7%, alternatively less than 0.3%, alternatively less than 1%, alternatively between 0.3% and 0.8%. The silicon-bonded hydroxyl groups formed during the preparation of polyorganosilicate resins can be converted to trihydrocarbon siloxane groups or to different hydrolyzable groups by reacting the silicone resin with a silane, disiloxane or disilazane containing appropriate end groups. The silane containing hydrolysable groups may be added in a molar excess in an amount exceeding that required to react with the silicon-bonded hydroxyl groups of the polyorganosilicate resin.

In one embodiment, the starting material D) is a polyorganosilicate resin comprising (D6) unit formula (R ²⁰ ₃ SiO _1/2 ) _c (R ²⁰ ₂ SiO _2/2 ) _d (SiO _4/2 ) _e wherein the subscripts c , d and e are mole fractions having values such that 0 < c < 0.6, 0 < d < 0.5, 0.4 < e <1; R ²⁰ is as described above, provided that at least one R ²⁰ per molecule is a hydrolysable group in (D6). Alternatively, the hydrolyzable group for R ²⁰ is selected from a hydroxyl group or an alkoxy group such as methoxy or ethoxy, alternatively the hydrolyzable group is a hydroxyl group.

A variety of suitable polyorganosilicate resins are available from Dow Silicones Corporation of Midland, Michigan, Momentive Performance Materials, Albany, NY, and Bluestar Silicones, East Brunswick, NJ. It is available from suppliers such as Bluestar Silicones USA Corp. For example, Dowsil™ MQ-1600 solid resin, Dowsil™ MQ-1601 solid resin, and Dowsil™ 1250 surfactant, Momentive SR-1000, all commercially available from Dow Silicones Corporation, Midland, Michigan, USA Wacker TMS-803 is suitable for use in the methods described herein. Alternatively, resins containing M, T and Q units may be used, such as Dowsil™ MQ-1640 flake resin, also commercially available from Dow Silicones Corporation. These resins may be supplied in an organic solvent.

Alternatively, the polysiloxane resin may comprise (D7) a silsesquioxane resin, ie a resin comprising T units of formula (R ²⁰ SiO _3/2 ), wherein R ²⁰ is as described above, provided that At least one R ²⁰ per molecule is a hydrolysable group in (D7). Silsesquioxane resins suitable for use herein are known in the art and commercially available. For example, methylmethoxysiloxane methylsilsesquioxane resin is commercially available as Dowsil™ US-CF 2403 resin from Dow Silicones Corporation of Midland, Michigan. Alternatively, the silsesquioxane resin may have phenylsilsesquioxane units, methylsilsesquioxane units, or a combination thereof. Such resins are known in the art and are commercially available as Dowsil™ 200 flake resin, also available from Dow Silicones Corporation. Alternatively, the silsesquioxane resin comprises D units of formula (R ⁸ ₂ SiO _2/2 ) and/or (R ⁸ X"SiO _2/2 ) and formulas (R ⁸ SiO _3/2 ) and/or ( It may further comprise T units of X"SiO _3/2 ), ie, DT resins, where R ⁸ and X" are as described above. DT resins are known in the art and are commercially available and include For example, methoxy functional DT resins include Dowsil™ 3074 and Dousyl™ 3037 resins; silanol functional resins include Dousyl™ 800 series resins, which are also commercially available from Dow Silicones Corporation. Other suitable resins include DT resins containing methyl and phenyl groups.

The starting material D) can be one silanol-functional organosilicon compound, or two or more silanol-functional organosilicon compounds differing in at least one of the following properties: structure, viscosity, average molecular weight, siloxane units and sequence. may include Alternatively, the starting material D) may comprise a mixture of two or more polyorganosilicate resins. Alternatively, the starting material D) may comprise a mixture of two or more silanol-functional polyorganosiloxanes, such as bis-hydroxyl-terminated polydiorganosiloxanes and polyorganosilicate resins. Alternatively, the starting material D) may comprise a mixture of silanol-functional silanes and silanol-functional polyorganosiloxanes. Alternatively, the starting material D) may comprise a mixture of two or more silsesquioxane resins.

The amount of starting material depends on various factors including the species of starting material D) selected and its silanol content. For example, when the starting material D) comprises a linear silanol-functional polydiorganosiloxane, a molar ratio of SiOH to cyclic siloxazane from 1:1 to 1:1.25 can be used. Alternatively, a 2% to 5% molar excess of cyclic siloxazane may be used relative to the silanol content of the starting material D), alternatively a molar excess of up to 20% silanol may be used. The stoichiometric addition of the cyclic siloxazanes to the silanol content of the starting material D-II) results in residual silanol-functional polyorganosiloxanes, terminal amino-functional polyorganosiloxanes, and silanols and organoamino-functional A reaction product mixture with a polyorganosiloxane having both ends can be provided. In the case of dendritic starting materials D-II), an average of 5% to 30% of residual silanol may not be consumed, and a maximum of more than 99% may typically be capped.

In the method for preparing the amino-functional organosilicon polyorganosiloxane described above, step 1) [combining the starting materials comprising A) and D)] may be performed by any convenient means, such as mixing, optionally With heating, it can be carried out. Mixing and heating may be carried out using any convenient means, such as loading the starting material into a vessel such as a reactive distillation apparatus or a stirred jacketed batch reactor with a jacketed reboiler, the jacket comprising It can be heated and cooled by passing steam/water or a heat transfer fluid through the jacket. The process may be carried out at a temperature of at least 50°C, alternatively at least 85°C, alternatively at least 90°C. Alternatively, the heating in step 1) may be carried out at 50°C to 150°C, alternatively 85°C to 150°C, alternatively 90°C to 150°C. This process is carried out for a time sufficient to form the amino-functional polyorganosiloxane.

In step 1), one of the starting materials A) and D) can be added continuously or incrementally to the vessel containing the other of the starting materials A) and D). Such addition may be performed manually or using metering equipment.

The methods described above may optionally further comprise one or more additional steps. The process may optionally further comprise step 3) of adding one or more additional starting materials to the reaction mixture in step 1). Alternatively, step 3) may be performed during and/or after step 1) and before step 2). The further starting material consists of E) an acid procatalyst, F) an aminoalkyl-functional alkoxysilane, G) an endblocker, H) a solvent, and a combination of two or more of E), F), G) and H). may be selected from the group.

Starting material E) acid procatalyst

The starting material E) in the process for preparing an amino group-terminated polydiorganosiloxane comprises an acid procatalyst. The acid procatalyst may be a carboxylic acid. Without wishing to be bound by theory, it is believed that the carboxylic acid will react with an amino-functional group (or α-alkoxy-ω-amino-functional polysiloxane described below, if present) in the cyclic polysiloxazane to form a carboxylate salt catalyst. It is considered The carboxylic acid may be selected from a wide range of carboxylic acids. The carboxylic acid may be, for example, an aliphatic carboxylic acid having from 1 to 20 carbon atoms, alternatively from 2 to 20 carbon atoms. For example, acetic acid, propionic acid, octanoic acid, decanoic acid or lauric acid are suitable for use in the present invention. Alternatively, aliphatic carboxylic acids substituted with hydrophilic groups such as hydroxyl, for example lactic acid, may be used. Alternatively, an electron-withdrawing moiety, for example a carboxylic acid substituted with a halogen such as fluorine or chlorine or a hydroxyl group, can be used, and Examples are lactic acid and fluoroalkanoic acid, such as fluoroacetic acid or 4,4,4-trifluorobutanoic acid. Other suitable carboxylic acids include benzoic acid, citric acid, maleic acid, myristic acid and salicylic acid. Alternatively, combinations of two or more of the above carboxylic acids may be used.

F) aminoalkyl-functional alkoxysilanes

The process for preparing the amino-functional polyorganosiloxane may optionally further comprise the step of adding the starting material F), an aminoalkyl-functional alkoxysilane. Without wishing to be bound by theory, F) adding the amino-functional alkoxysilane produces an amino-functional organosilicon product, which may be an amino group-terminated polyorganosiloxane further comprising pendant amino-functional groups. It is believed to provide

The starting material F) contains an aminoalkyl group and an alkoxy group bonded to Si. The aminoalkyl group may have the formula (F1): R ¹³ -(NH-A′) _q -NH-A-, wherein A and A′ each independently have 1 to 6 carbon atoms and optionally an ether linkage group linear or branched alkylene groups containing; the subscript q is 0 to 4; R ¹³ is hydrogen, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. Alternatively, R ¹³ can be hydrogen; q can be 0 or 1; A and A' (if present) each contain 2 to 4 carbon atoms. Examples of suitable aminoalkyl groups include -(CH ₂ ) ₃ NH ₂ , -(CH ₂ ) ₄ NH ₂ , -(CH ₂ ) ₃ NH(CH ₂ ) ₂ NH ₂ , —CH ₂ CH(CH ₃ )CH ₂ NH(CH ₂ ) ₂ NH ₂ ,

-(CH ₂ ) ₃ NHCH ₂ CH ₂ NH(CH ₂ ) ₂ NH ₂ , -CH ₂ CH(CH ₃ )CH ₂ NH ₂ , -CH ₂ CH(CH ₃ )CH ₂ NH(CH ₂ )3NH ₂ ,

를 가질 수 있고, 여기서 A, A', R¹³ 및 하첨자 q는 상기에 정의된 바와 같고; R'는 1 내지 6개의 탄소 원자를 갖는 알킬 기 또는 알콕시알킬 기, 예를 들어, 메틸, 에틸, 부틸 또는 메톡시에틸이고; R¹⁴ 및 R¹⁵는 각각 독립적으로 -OR' 기 또는 선택적으로 치환된 알킬 기 또는 아릴 기이다. 대안적으로, 선형 폴리다이오르가노실록산의 제조에 있어서, R¹⁴ 기는 알킬 기, 예컨대 메틸일 수 있고, R¹⁵ 기는 화학식 -OR', 예컨대 메톡시 또는 에톡시를 가질 수 있다. 출발 재료 F)에 적합한 아미노알킬-작용성 알콕시실란의 예에는 F3) 3-아미노프로필메틸 다이메톡시실란, F4) 3-아미노프로필메틸 다이에톡시실란, F5) 아미노에틸-아미노아이소부틸 메틸 다이메톡시 실란, F6) 아미노에틸-아미노아이소부틸 메틸 다이에톡시실란, F7) 3-아미노프로필다이메틸 에톡시실란, F8) 3-아미노프로필다이메틸 메톡시실란, F9) 3-(2-아미노에틸아미노)프로필-다이메톡시메틸실란, F10) 3-(2-아미노에틸아미노)프로필-다이에톡시메틸실란, F11) 아미노프로필 메틸 다이메톡시 실란, F12) 아미노프로필 메틸 다이에톡시실란, 및 F13) F3) 내지 F12) 중 둘 이상의 조합이 포함된다. 일 실시 형태에서, 아미노알킬-작용성 알콕시실란은 모노알콕시실란, 예컨대 F7) 3-아미노프로필다이메틸 에톡시실란 또는 F9) 3-아미노프로필다이메틸 메톡시실란을 포함하고, 아미노-작용성 폴리다이오르가노실록산은 이로부터의 아미노-작용성 펜던트 기를 갖는다.—(CH ₂ ) ₃ NH(CH ₂ ) ₄ NH ₂ and —(CH ₂ ) ₃ O(CH ₂ ) ₂ NH ₂ . Alkoxy groups bonded to Si may contain non-reactive substituents or linking groups, such as ether linkages. The aminoalkyl-functional alkoxysilane has the formula (F2):

wherein A, A', R ¹³ and the subscript q are as defined above; R' is an alkyl or alkoxyalkyl group having 1 to 6 carbon atoms, for example methyl, ethyl, butyl or methoxyethyl; R ¹⁴ and R ¹⁵ are each independently an —OR′ group or an optionally substituted alkyl group or aryl group. Alternatively, in preparing a linear polydiorganosiloxane, the R ¹⁴ group may be an alkyl group such as methyl and the R ¹⁵ group may have the formula —OR′, such as methoxy or ethoxy. Examples of aminoalkyl-functional alkoxysilanes suitable for the starting material F) include F3) 3-aminopropylmethyl dimethoxysilane, F4) 3-aminopropylmethyl diethoxysilane, F5) aminoethyl-aminoisobutyl methyl die Methoxy silane, F6) aminoethyl-aminoisobutyl methyl diethoxysilane, F7) 3-aminopropyldimethyl ethoxysilane, F8) 3-aminopropyldimethyl methoxysilane, F9) 3-(2-amino) Ethylamino)propyl-dimethoxymethylsilane, F10) 3-(2-aminoethylamino)propyl-diethoxymethylsilane, F11) aminopropyl methyl dimethoxy silane, F12) aminopropyl methyl diethoxysilane, and F13) a combination of two or more of F3) to F12). In one embodiment, the aminoalkyl-functional alkoxysilane comprises a monoalkoxysilane, such as F7) 3-aminopropyldimethyl ethoxysilane or F9) 3-aminopropyldimethyl methoxysilane, and the amino-functional poly The diorganosiloxane has amino-functional pendant groups therefrom.

Starting material G) endblockers

The process for preparing an amino-functional organosilicon compound, such as an amino-functional polyorganosiloxane [prepared when starting materials D-II) is used in the process described above, optionally comprises starting material G), an endblocker It may further include the step of adding. Without wishing to be bound by theory, for example, an amino-functional polydiorganosiloxane to be prepared by the methods described herein may be partially trihydrocarbylsilyl-terminated (e.g., trialkyl-silyl- It is believed that when having terminated, such as trimethylsilyl-terminated) groups and some amino-functional groups, a terminal blocker can be used to cap some of the silanol groups on the starting material D-II). The endblocking agent can react with a silanol group to produce an endblocking triorganosilyl unit, wherein the triorganosilyl functional group is unreactive with the silanol group of the starting material A). Suitable endblocking agents are exemplified by (G1) monoalkoxysilanes, (G2) silazanes, or (G3) both (G1) and (G2).

(G1) monoalkoxysilane may have the formula (G4): R ¹⁶ ₃ SiOR ¹⁷ , wherein each R ¹⁶ is independently a monovalent organic group that is unreactive with a silanol functional group, and each R ⁵ is 1 to It is a monovalent hydrocarbon group of 6 carbon atoms. Alternatively, R ¹⁷ may be an alkyl group of 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms, alternatively 1 or 2 carbon atoms, alternatively R ¹⁷ may be methyl. Each R ¹⁶ may be a monovalent hydrocarbon group selected from alkyl, alkenyl and aryl groups. Alternatively, each R ¹⁶ can be an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, or a phenyl group. Alternatively, each R ¹⁶ can be an alkyl group of 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms, and alternatively each R ¹⁶ can be methyl. Examples of the monoalkoxysilane for the starting material (G1) include (G5) trimethylmethoxysilane and (G6) trimethylethoxysilane.

Suitable (G2) silazanes may have the formula (G7): (R ¹⁸ R ¹⁹ ₂ Si) ₂ NH, wherein each R ¹⁸ is a monovalent hydrocarbon group (as described herein for R ⁸ ) and independently selected from monovalent halogenated hydrocarbon groups (eg, a monovalent hydrocarbon group of R ⁸ wherein at least one hydrogen is replaced by a halogen atom such as Cl or F), and each R ¹⁹ is as described above for R ¹⁷ . is an independently selected monovalent hydrocarbon group of 1 to 6 carbon atoms as Each R ¹⁸ may be an alkyl group, an alkenyl group or a halogenated alkyl group. Suitable alkyl groups for R ¹⁸ include methyl, ethyl, propyl and butyl. Suitable alkenyl groups include vinyl and allyl. Suitable halogenated alkyl groups include trifluoropropyl. Examples of suitable silazanes for the starting material (G2) include (G8) hexamethyldisilazane, (G9) sym-tetramethyldivinyldisilazane, and (G10) [(CF ₃ CH ₂ CH ₂ )(CH ₃ ) ) ₂ Si] ₂ NH.

The endblocker is optional, and the exact amount will depend on a variety of factors including the desired structure and amine content of the amino-functional polyorganosiloxane to be formed. However, the endblocker may be added in an amount of up to 5%, alternatively from 0.1% to 5%, based on the total weight of all starting materials used in this process. If present, all or part of the starting material G) may be added in step 1). Alternatively, a first portion of starting material G) may be added in step 1) and a second portion of starting material G) to be added in a further step added to the method after step 1) and before step 2). can

starting material H) solvent

The method for preparing the amino-functional organosilicon compound may optionally further comprise the step of adding the starting material H), a solvent. This solvent may be as described above for the starting material e) in the process for preparing the cyclic polysiloxazane. Without wishing to be bound by theory, it is believed that when a polysiloxane resin is selected for this purpose, a solvent may be used to introduce one or more starting materials, such as starting materials D-II). This process may use 0% to 200% solvent based on the total weight of all starting materials in the process. Alternatively, 0% to 90% solvent (same basis) may be used. Whether a solvent is used depends on various factors, including the choice of the starting material D). For example, a solvent may be used when a silanol-functional polyorganosiloxane resin which is solid at room temperature is selected as the starting material D). Alternatively, the process can be carried out neat if the starting material D) is a silanol-functional silane and/or a silanol-functional polydiorganosiloxane which is liquid at room temperature.

The method for preparing the amino-functional polyorganosiloxane may optionally further comprise one or more additional steps in addition to the steps described above. For example, the process comprises a step 4 of removing the residual acid [E) if an acid procatalyst is added] prior to and/or during step 2) of recovering the amino-functional polyorganosiloxane from the reaction mixture. ) may be additionally included. The amino-functional polyorganosiloxane may be recovered from the reaction mixture by any convenient means, such as stripping and/or distillation, optionally under vacuum. One or more of these method steps may be performed under an inert atmosphere, such as nitrogen.

The method for preparing the amino-functional polyorganosiloxane may optionally further comprise quenching unreacted cyclic polysiloxazane, unreacted silanol-functional polyorganosiloxane, or both. have. Quenching can be carried out by adding a starting material selected from the group consisting of I) water and B) an alcohol of formula R ¹⁰ OH, wherein R ¹⁰ is an alkyl group of 1 to 8 carbon atoms. Quenching can be carried out at any time after step 1) in the process for preparing the amino-functional polyorganosiloxane, alternatively before step 2).

B. Methods of Making Alkoxy-Functional Capping Agents

Alternatively, the cyclic polysiloxazane described above can be further reacted to prepare an α-alkoxy-ω-amino-functional polysiloxane useful as a capping agent, followed by adding, for example, the capping agent to the D) silanol-functionalized agent described above. organosilicon compounds such as D-II) silanol-functional polyorganosiloxanes. A process for preparing an α-alkoxy-ω-amino-functional polysiloxane comprises:

I)

A) a cyclic polysiloxazane prepared by the method described above, and

B) combining starting materials comprising an alcohol of formula R ¹⁰ OH, wherein R ¹⁰ is an alkyl group of 1 to 8 carbon atoms,

(여기서, 각각의 R⁸, R⁹, R¹⁰ 및 하첨자 x는 상기에 기재된 바와 같음)의 α-알콕시-ω-아미노-작용성 폴리실록산을 포함하는 반응 생성물을 제조하는 단계; 및C) chemical formula

preparing a reaction product comprising an α-alkoxy-ω-amino-functional polysiloxane of (wherein each of R ⁸ , R ⁹ , R ¹⁰ and the subscript x is as described above); and

optionally II) purifying the reaction product to recover C) α-alkoxy-ω-amino-functional polysiloxane.

Alternatively, in the α-alkoxy-ω-amino-functional polysiloxane, each R ⁸ can be an alkyl group, such as methyl, and each R ⁹ can be hydrogen. The starting material B) in this process, the alcohol, may be selected from the group consisting of methanol and ethanol.

The process described above produces α-alkoxy-ω-primary amino-functional polysiloxanes of the formula:

, 상기 식에서, 각각의 R⁸, R⁹ 및 R¹⁰, 및 하첨자 x는 상기에 기재된 바와 같다. 대안적으로, 각각의 R⁸은 1 내지 18개의 탄소 원자의 독립적으로 선택된 알킬 기, 대안적으로 메틸일 수 있다. 대안적으로, 각각의 R⁹는 수소일 수 있다. 대안적으로, 각각의 R¹⁰은 메틸 또는 에틸일 수 있다.

, wherein each of R ⁸ , R ⁹ and R ¹⁰ , and the subscript x are as described above. Alternatively, each R ⁸ can be an independently selected alkyl group of 1 to 18 carbon atoms, alternatively methyl. Alternatively, each R ⁹ can be hydrogen. Alternatively, each R ¹⁰ can be methyl or ethyl.

C. Alternative Methods of Making Amino-Functional Polyorganosiloxanes

The α-alkoxy-ω-amino-functional polysiloxanes described above are useful in alternative methods of preparing amino-functional organosilicon compounds, which include

One)

의 α-알콕시-ω-아미노-작용성 폴리실록산; 및The reaction product formed in step I) of the process described above and/or the formula purified in step II)

α-alkoxy-ω-amino-functional polysiloxanes of and

D) combining starting materials comprising a silanol-functional organosilicon compound (as described above) to prepare a reaction mixture;

optionally 2) heating the reaction mixture to 150° C. or less, alternatively 90° C. or less, alternatively 90° C. to 150° C.; and

3) adding E) acid procatalyst to the reaction mixture. This process may optionally further comprise a step 4) of F) adding an aminoalkyl-functional alkoxysilane to the reaction mixture. Starting material D), starting material E) and starting material F) and their amounts are as described above. Without wishing to be bound by theory, the step of starting material E) adding an acid precatalyst may be optional when the process is carried out above 90° C. case is considered to be carried out.

In the process for preparing the amino-functional organosilicon compound, mixing and heating use any convenient means, such as loading the starting material into a vessel such as a reactive distillation apparatus or a stirred jacketed batch reactor with a jacketed reboiler. The jacket can be heated and cooled by passing steam/water or a heat transfer fluid through the jacket. The starting materials and/or reaction mixture may be maintained at room temperature or heated to 150° C. or lower to facilitate the reaction, alternatively to 90° C. or lower. This process is carried out for a time sufficient to form the amino-functional organosilicon compound.

In steps 1) and 2), one of starting material A) and starting material D) can be added continuously or incrementally to the vessel containing the other of starting material A) and starting material D). Such addition may be performed manually or using metering equipment.

The methods described above may optionally further comprise one or more additional steps. The process may optionally further comprise step 4) of adding further starting materials to the reaction mixture in step 1) and/or step 2). The additional starting material may be selected from the group consisting of F) aminoalkyl-functional alkoxysilanes, G) endblockers, H) solvents, and combinations of two or more of F), G) and H). Alternatively, step 4) may be performed during and/or after step 1), before and/or after step 2), or before and/or during step 3). Starting material D), starting material E), starting material F), starting material G) and starting material H) are as described above. The method of making the amino-functional organosilicon compound optionally further comprises the step of quenching unreacted α-alkoxy-ω-amino-functional polysiloxane, unreacted silanol-functional organosilicon compound, or both. may include Quenching can be carried out by adding a starting material selected from the group consisting of I) water and B) an alcohol of formula R ¹⁰ OH, wherein R ¹⁰ is an alkyl group of 1 to 8 carbon atoms. Quenching can be carried out at any time after step 1), alternatively before recovery of the amino-functional polyorganosiloxane. The amino-functional polyorganosiloxane may be recovered from the reaction mixture by stripping and/or distillation, optionally under vacuum. One or more of these method steps may be performed under an inert atmosphere, such as nitrogen. For example, steps 1) and 2) described above may optionally further comprise flowing an inert gas through the vessel headspace. Without wishing to be bound by theory, it is believed that flowing an inert gas through the reactor headspace can help remove odors and low boiling point impurities from the system.

III. Amino-functional polyorganosiloxanes

The method described above produces amino-functional polyorganosiloxanes. When a silanol-terminated polydiorganosiloxane is used as starting material D-II), the amino-functional polyorganosiloxane is an amino group-terminated polydiorganosiloxane. When each R ⁹ is hydrogen, the amino group-terminated polydiorganosiloxane has the formula:

의 1차 아미노 기-말단화된 폴리다이오르가노실록산이며, 여기서 R¹²는 OH, R⁸ 및 -CH₂CH(R⁹)CH₂NH₂로 이루어진 군으로부터 선택되고, 하첨자 n = (x + y + 1)이다. 대안적으로, R¹²는 OH, R⁸ 및 -CH₂CH₂CH₂NH₂로 이루어진 군으로부터 선택될 수 있다.

is a primary amino group-terminated polydiorganosiloxane of wherein R ¹² is selected from the group consisting of OH, R ⁸ and —CH ₂ CH(R ⁹ )CH ₂ NH ₂ , and the subscript n = (x + y + 1). Alternatively, R ¹² may be selected from the group consisting of OH, R ⁸ and —CH ₂ CH ₂ CH ₂ NH ₂ .

Alternatively, when a silanol-functional polysiloxane resin is used as the starting material D), the amino-functional polyorganosiloxane is an amino-functional polyorganosiloxane resin. When each R ⁹ is hydrogen, the amino-functional polyorganosiloxane resin is a primary amino-functional polyorganosiloxane resin. The primary amino-functional polyorganosiloxane resin has the unit formula:

[(H ₂ NCH ₂ CH ₂ CH)R ⁸ ₂ SiO _1/2 ] _J [(H ₂ NCH ₂ CH ₂ CH)R ⁸ SiO _2/2 ] _K [(H ₂ NCH ₂ CH ₂ CH)SiO _{3/ 2} ] _L (R ²⁰ ₃ SiO _1/2 ) _G (R ²⁰ ₂ SiO _2/2 ) _H (R ²⁰ SiO _3/2 ) _F (SiO _4/2 ) _D , wherein R ⁸ and R ²⁰ is as described above, subscript D is as described above, subscript G ≤ A, subscript H ≤ B, and subscript F ≤ C. The subscript G ≥ 0, the subscript H ≥ 0, the subscript F ≥ 0, and the subscript D ≥ 0. Quantity (J + K + L) > 1. Quantity (L + F + D) > 1. The quantity (J + K + L + G + H + F + D) has a value sufficient to provide the resin from 1,000 g/mole to 12,000 g/mole of Mn.

personal care products

The amino-functional polyorganosiloxanes described above (eg, amino-functional polydiorganosiloxanes) can be formulated into personal care products. In general, such products can be made at room temperature using a simple propeller mixer, a Brookfield counter-rotating mixer, or a homogenizing mixer if no material that is solid at room temperature is present. No special equipment or processing conditions are typically required. Depending on the type of form produced, the preparation method will be different, but such methods are known in the art.

Personal care products may be functional, cosmetic, therapeutic, or some combination thereof with respect to the body part to which they are applied. Typical examples of such products include antiperspirants and deodorants, skin care creams, skin care lotions, moisturizers, facial treatments such as acne or wrinkle removers, personal and facial cleansers, bath oils, perfumes, colognes, sachets, sunscreens, cotton Conductive and post-shaving lotions, shaving soaps and shaving foams, hair shampoos, hair conditioners (either residual or rinse), hair colorants, hair relaxants, hair styling aids such as sprays, fixatives, mousses and/or or gel; Permanent, depilatory, and cuticle coat, makeup, color cosmetics, foundation, concealer, blush, lipstick, eyeliner, mascara, oil remover, color makeup remover, powder, medicinal cream, dental hygiene, antibiotic, healing promoting pastes or sprays (which may be prophylactic and/or therapeutic), including but not limited to In general, personal care products include any conventional, including, but not limited to, liquids, rinses, lotions, creams, pastes, gels, foams, mousses, ointments, sprays, aerosols, soaps, sticks, soft solids, solid gels and gels. It may be formulated with a carrier that permits application in the phosphorus form. What constitutes a suitable carrier will be apparent to those skilled in the art.

Amino-functional polyorganosiloxanes can be used in a variety of personal, household and healthcare applications. In particular, amino-functional polydiorganosiloxanes are disclosed in US Pat. Nos. 6,051,216 to Barr et al; US Pat. No. 5,919,441 to Mendolia et al.; US Pat. No. 5,981,680 to Petroff et al.; U.S. Patent Application No. 2010/0098648 to Yu; and in personal care products disclosed in International Patent Publication No. WO 2004/060101; in sunscreen compositions as disclosed in US Pat. No. 6,916,464 to Hansenne et al.; in a cosmetic composition also containing a film-forming resin as disclosed in U.S. Patent Publication No. WO2003/105801; U.S. Patent Application 2003/0235553 to Lu, U.S. Patent Application 2003/0072730 to Tornilhac, U.S. Patent Application 2003/0170188 to Ferrari et al., European Patent Application No. Tonilhac 1,266,647, European Patent No. 1,266,648 to Ferrari et al., European Patent No. 1,266,653 to Ferrari et al., International Patent Publication No. WO2003/105789 by Ru, International Patent Publication No. WO2004/000247 by Ru, and International Patent Publication No. WO2003/106614 by Ru in a cosmetic composition as disclosed in as an additional agent to those disclosed in WO2004/054523 of tonylac; in lasting cosmetic compositions as disclosed in US Patent Application Publication No. 2004/0180032; and in transparent or translucent care and/or makeup compositions as discussed in WO 2004/054524; All of these are incorporated herein by reference.

Alternatively, the amino-functional polyorganosiloxane may be used as part of a colorant or fixative composition and applied as a pre-treatment, intermediate treatment, or post-treatment in the process of coloring or perming hair. This purpose can range from color maintenance and color enhancement to reconditioning pigmented hair fibers. Examples are given in patents, namely, US Patent Application Publication No. 2003/0152534 to Legrand et al., US Patent Application Publication No. 2003/0152541 to Legrand et al., and US Patent Application Publication No. 2003/0147840 to Legrand et al. , U.S. Patent No. 6,953,484 to Devin-Baudoin et al., U.S. Patent No. 6,916,467 to Devin-Baudoin et al., U.S. Patent Application Publication No. 2004/0045098 to Devin-Baudoin et al., Devin - U.S. Patent Application Publication No. 2003/0126692 by Baudoin et al., International Patent Publication No. WO2007/071684 of Audousset acquired by L'Oreal, and U.S. Patent Application Publication No. 2008/ 0282482, and US Pat. No. 7,335,236 to McKelvey assigned to Noxell Corp., all of which are incorporated herein by reference.

The personal care product according to the invention is applied to the human body, for example skin or hair, by standard methods, for example using an applicator, a brush, applied by the hand and/or poured on it, Possibly this product can be used by rubbing or massaging it onto or into the human body. Removal methods, for example removal methods for color cosmetics, are also well known standard methods including washing, wiping and peeling. For use on the skin, the personal care product according to the invention can be used, for example, in a conventional manner for conditioning the skin. An effective amount of the product for this purpose is applied to the skin. Such effective amounts generally range from 1 mg/cm 2 to 3 mg/cm 2 . Application to the skin typically involves acting the composition into the skin. Such methods for application to the skin include contacting the skin with an effective amount of the composition and then rubbing the composition into the skin. These steps may be repeated as many times as necessary to achieve the desired effect.

The use on the hair of a personal care product according to the present invention may use the conventional manner for conditioning the hair. An effective amount of a product for conditioning the hair is applied to the hair. Such effective amounts generally range from 0.5 g to 50 g, alternatively from 1 g to 20 g. Application to hair typically involves applying the composition through the hair such that most or all of the hair is in contact with the product. This method for conditioning hair includes applying to the hair an effective amount of a hair care product, and then allowing the composition to act through the hair. These steps may be repeated as many times as necessary to achieve the desired conditioning effect.

Non-limiting examples of additives that may be formulated into personal care products in addition to amino-functional polyorganosiloxanes include (i) additional silicones, (ii) anti-acne agents, (iii) anti-caries agents, (iv) anti-dandruff agents. agents, (v) antioxidants, (vi) biocides, (vii) botanical agents, (viii) cleansing agents, (ix) colorants, (x) conditioning agents, (xi) depositing agents, such as cationic deposition aids, (xii) electrolytes, (xiii) emollients, (xiv) exfoliants, (xv) foam boosters, (xvi) fragrances, (xvii) humectants, (xviii) sealants, (xix) oils, (xx) insecticides, (xxi) ) pH modifiers, (xxii) pigments, (xxiii) preservatives, (xxiv) rheology modifiers, (xxv) solvents, (xxvi) stabilizers, (xxvii) stabilizers, (xxviii) sunscreens, (xxix) surfactants, (xxx) suspending agents, (xxxi) tanning agents, (xxxii) thickening agents, (xxxiii) vitamins, (xxxiv) waxes, (xxxv) wound healing promoters, and (xxxvi) any two or more of (i) to (xxxv) This is included.

Example

These examples are intended to illustrate the invention to those skilled in the art, and should not be construed as limiting the scope of the invention as set forth in the claims. Table 2 below shows the starting materials used in these examples.

[Table 2]

Part I. Synthesis of cyclic polysiloxazanes

In this Reference Example 1, the accelerator allyloxy-di-(2,4,6-trimethylphenyl)silane was synthesized as follows. 5.1302 g of chloro-di-(2,4,6-trimethylphenyl)silane was added to a 250 mL flask and dissolved in 110 mL pentane. In a separate flask, 1.0328 g of allyl alcohol and 1.9709 g of triethylamine were combined and mixed. This mixture was then added to chloro-di-(2,4,6-trimethylphenyl)silane over 1 hour, causing a large amount of white precipitate to form. The flask contents were stirred for 2 hours. The solid material was filtered and the supernatant liquid was collected. The solid was washed with 10 mL of pentane, which was combined with the supernatant liquid. The low boiling volatiles were stripped under vacuum to give a cloudy liquid, which was dissolved in 60 mL of pentane, filtered again, stripped and collected as liquid 4.7018 g of allyloxy-di-(2,4,6-trimethylphenyl) ) silane was provided. The product was characterized by ¹ H NMR, ²⁹ Si NMR and GC-mass spectrometry.

In this Reference Example 2, the accelerator allyloxy-methyl-(2,4,6-triisopropylphenyl)silane was synthesized as follows. 30 mL of toluene was added to 250 mL and the half-jacket flask was cooled to about -11°C. 4.9554 g (43.1 mmol) of dichloromethylsilane were added. Next, 25 mL of 0.5 M 2,4,6-triisopropylphenylmagnesium bromide was slowly added to the flask over 45 minutes, which gave a pale yellow solution and a colorless precipitate. The contents of the flask were cooled with stirring for 1 hour and then allowed to warm to ambient temperature, where the contents were stirred for another 1 hour. Next, 3.2534 g of 1,4-dioxane was added to the flask. A large amount of white precipitate was allowed to form and the flask contents were stirred for 1 hour. The salt was filtered from the supernatant liquid. The solid was washed with 30 mL of pentane, which was combined with other liquids. The volatile components were removed under vacuum to give 2.9466 g of a white microcrystalline solid. The product was identified as chloro-methyl-(2,4,6-triisopropylphenyl)silane. The product was characterized by ¹ H NMR, ²⁹ Si NMR and GC-mass spectrometry.

2.7908 g of chloro-methyl-(2,4,6-triisopropylphenyl)silane was added to a 250 mL half-jacketed flask, dissolved in 40 mL pentane, and cooled to about 4°C. In a separate flask, 0.6016 g of allyl alcohol, 1.078 g of triethylamine and 4.7 g of pentane were combined and mixed. This mixture was then added to chloro-methyl-(2,4,6-tri-isopropylphenyl)silane over 25 min. During this time, the flask contents were warmed to 9.8° C. and a large amount of white precipitate formed. The flask contents were warmed to ambient temperature and stirred for 2 hours. The solid material was filtered and the supernatant liquid was collected. The solid was washed with 10 mL of pentane, which was combined with the supernatant liquid. The low boiling volatiles were stripped under vacuum to give a cloudy liquid, which was again filtered and collected as allyloxy-methyl-(2,4,6-triisopropylphenyl)silane. The product was characterized by ¹ H NMR, ²⁹ Si NMR and GC-mass spectrometry.

In this Reference Example 3, the accelerator (1-methyl-2-propin-1-yl)oxy-diphenylsilane was synthesized as follows. 9.9272 g of chlorodiphenylsilane was added to a 250 mL half-jacketed flask, dissolved in 100 mL pentane, and cooled to about 1°C. In a separate flask, 3.222 g of 1-methyl-prop-2-yn-1-ol, 4.6258 g of triethylamine and 3.0000 g of pentane were combined and mixed to give a yellow solution. This mixture was then added to chlorodiphenylsilane over 30 minutes. During this time, the flask contents were warmed to 8.9° C. and a large amount of white precipitate formed. The flask contents were warmed to room temperature and stirred for 2 hours. The solid material was filtered and the supernatant liquid was collected. The solid was washed twice with 30 mL of pentane and the wash combined with the supernatant liquid. The low boiling volatile components were stripped under vacuum to give a cloudy liquid. The liquid was then combined with 15 mL of pentane, stirred and filtered to give a clear liquid. The liquid was stripped under reduced pressure to give 10.2342 g of a pale yellow clear liquid consisting of (1-methyl-2-propin-1-yl)oxy-diphenylsilane. The product was characterized by ¹ H NMR, ²⁹ Si NMR and GC-mass spectrometry.

In this Reference Example 4, a stock solution of a soluble platinum source, such as Karstedt's catalyst [Pt ₂ O(SiMeVi) ₃ ] or Ashby's catalyst [Pt (SiMeViO) ₄ ], was mixed with the promoter at room temperature to obtain a Pt-promoter catalyst solution. was prepared. The reactivity is evident in the exothermic as well as the rapid color change from a colorless or pale yellow solution to a typically orange to dark red solution. This mixture is ready for use within 1 hour to 3 days depending on the accelerator used. This mixture was characterized by ¹ H, ²⁹ Si and ¹⁹⁵ Pt NMR. The combinations of Pt-promoter stock solutions evaluated are provided in Table 3 below.

[Table 3]

In this Example 5, a cyclic siloxazane of the formula -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- was prepared by the method of the present invention in which the molar ratio of allylamine to TMDSO is 2:1 or more and TMDSO is added to allylamine. . The amounts are provided in the table below. First, the Pt-promoter solution was mixed at room temperature with allylamine and optional solvent in a glass reaction flask equipped with a thermocouple, magnetic stir bar and a condenser cooled to -5°C to -20°C. The allylamine/catalyst solution was then heated to reflux. TMDSO was fed to this mixture over time and a large amount of hydrogen was produced in an instant after addition, typically less than 5 seconds. The solution temperature was gradually increased as long as heat was applied to the system during the addition of TMDSO and also when the supply of TMDSO was stopped. After completion of the feed of TMDSO, the mixture was set to a predetermined temperature, stirred for 1 hour to 5 hours, and then cooled to room temperature. The product, cyclic siloxazane, -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH-, was characterized by GC-FID, GC-MS, ¹ H NMR and/or ²⁹ Si NMR. The cyclic siloxazane, -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH-, was purified by the distillation method described in EP 0 342 518 A2 to give isolated yields of 65% to 85%.

[Table 4]

In this Example 6, the molar ratio of allylamine to TMDSO is from 1:1 to less than 1:2 and by the inventive process of adding TMDSO to allylamine, the cyclic silox of formula -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- Sazan was prepared. The amounts are provided in the table below. First, the Pt-promoter solution was mixed at ambient temperature with allylamine and optional solvent in a glass reaction flask equipped with a thermocouple, magnetic stir bar and a condenser cooled to -5°C to -20°C. The allylamine/catalyst solution was then heated to reflux. TMDSO was fed to this mixture over time and a large amount of hydrogen was generated in an instant after addition, typically less than 5 seconds. The solution temperature increased gradually during the addition of TMDSO until it reached a temperature of 70°C to 110°C, but also gradually increased as long as heat was applied to the system even when the supply of TMDSO was stopped. After completion of the feed of TMDSO, the mixture was set at a temperature of 60° C. to 120° C., stirred for 30 minutes to 8 hours, and then cooled to room temperature. The product, cyclic siloxazane, -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH-, was characterized by GC-FID, GC-MS, ¹ H NMR and/or ²⁹ Si NMR. The cyclic siloxazane, -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH-, was purified by the distillation method described in EP 0 342 518 A2, which gave isolated yields of 65-85%.

In this comparative example 7, the example of EP 0 342 518 A2 did not complete the 1:1 TMDSO to allylamine process safely or in any reasonable yield. The report states:

"Allylamine and TMDS (TMDSO) in a 1:1 molar ratio were combined with 40 ppm of catalyst in a nitrogen atmosphere, where hydrogen evolution was immediately observed. The mixture was heated to reflux and the pot temperature was increased from 43° C. over 65 minutes. The temperature was raised to 73° C.; then an exothermic reaction occurred which caused an immediate rise to 155° C. The mixture was cooled to 45° C. and distilled under vacuum to obtain a very small proportion of cyclic disiloxazane. Steam distillation and found to be a mixture of bis(3-aminopropyl)polydimethylsiloxane".

In this comparative example 8, the slow addition of TMDSO containing about 100 ppm Pt (SiMeViO) ₄ catalyst to allylamine did not provide a complete reaction, instead almost no product above 55% conversion was produced even after 6 hours of mixing. Instead, a fine black powder began to precipitate. GC-FID confirmed incomplete conversion to cyclic siloxazanes.

In this Example 9, TMDSO, Pt catalyst and promoter are added to a suitably sized glass reaction flask equipped with a thermocouple, magnetic stir bar, and a condenser cooled to -5°C to -20°C by the method of the present invention. -SiMe ₂ OSiMe ₂ C ₃ H ₆ A cyclic siloxazane of NH- was prepared. The solution was heated to a temperature between 40°C and 75°C. The amounts are provided in the table below. The Pt catalyst and promoter were mixed together prior to addition to TMDSO or added separately to TMDSO. The combination of reagents turned the solution yellow. Allylamine was fed to this mixture over time and a large amount of hydrogen was generated in an instant after addition, typically less than 5 seconds. An exotherm was also present, controlled by the feed rate of allylamine and the rate of cooling through the wall of the reaction flask. The reaction flask temperature was maintained at a temperature between 50° C. and 110° C. by controlling the exotherm and by adding heat into the system after stopping the feed of TMDSO. After completion of the feed of TMDSO, the mixture was set to a temperature of 60° C. to 120° C., stirred for 30 minutes to 4 hours, and then cooled to room temperature. The product, cyclic siloxazane, -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH-, was characterized by GC-FID, GC-MS, ¹ H NMR and/or ²⁹ Si NMR. The cyclic siloxazane, -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH-, was purified by the distillation method described in EP 0 342 518 A2 to give an isolated yield of 65% to 85%.

In Comparative Example 10, a cyclic siloxazane of the formula -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- was synthesized by a method similar to that described in US Patent No. 5,026,890 but with some changes as follows. To a 250 mL flask equipped with a glass thermowell and a cooled reflux condenser were added 0.0224 g of 0.104 M Pt (SiMeViO) ₄ (about 2% Pt) and 5.8641 g allyl-amine. The mixture was heated to reflux (Δ ₀ = 53.4° C.). 6.8820 g of 1,1,3,3-tetramethyldisiloxane (TMDSO) to test and minimize the amount of non-hydrosilylated intermediate (NHI) of formula H ₂ C=CHCH ₂ NHSiMe ₂ OSiMe ₂ H was added little by little. This method step deviates from the example of US Pat. No. 5,026,890 where TMDSO was added in one aliquot. The reason for this change is that the bulk addition of TMDSO to allyl-amine produces quantitative amounts of flammable, incompressible hydrogen gas, which is associated with a huge and spontaneous pressure increase and limited emissions for safe handling of toxic allyl-amine amines. This is because it cannot be supported in a large production reactor due to safety concerns. As TMDSO was added, the reflux temperature rose slowly. After 3 hours, about 70% TMDSO was added and the temperature was raised to 61.5°C. The flask contents were analyzed by CG and showed that mainly NHI was formed and only about 4% was converted to hydrosilylated cyclic -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH-.

Heating was stopped overnight and the solution was stirred overnight at ambient temperature. The next day, heating to reflux was resumed. After 1.5 hours, the remaining TMDSO was added and heating continued for another 9.5 hours, in which case the temperature rose to 73.9°C. Heating was stopped and the solution was stirred at room temperature overnight.

The next day, the solution was heated to reflux for 9 hours, in which case the temperature reached 106.1°C. This also deviates from the method described in US Pat. No. 5,026,890, in which the method is practiced during one block of heating. The heat source was removed for safety reasons that unreacted components remain at elevated temperature, and experiments have already demonstrated that the conversion rate is poor. The additional time to complete this method demonstrated that the method described in US Pat. No. 5,026,890 was unreliable and sluggish. Analysis by GC showed that 95+% of the NHI was converted to a cyclic siloxazane of the formula -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH-. This comparative example showed that the process of US Pat. No. 5,026,890 was not suitable for commercial scale operation due to safety concerns and insufficient conversion to be achieved for the desired reaction time.

In this Example 11, a cyclic siloxazane of the formula -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- was prepared by the method of the present invention as follows. First, about 0.1284 g of a solution containing 0.02 M Pt (1,1,3,3-tetramethyl-divinyl-disiloxane complex) and allyloxydiphenylsilane (prepared as described in Reference Example 5) was prepared To 5.8710 g of allylamine in a 250 mL flask equipped with a glass thermowell and a cold reflux condenser. The mixture was heated to reflux (Δ ₀ = 53.2° C.). 6.8902 g of TMDSO was added to the flask in small portions. After 2 hours, about 70% TMDSO was added and the temperature was raised to 65.4°C. The solution was allowed to cool to ambient temperature and analyzed by GC-FID, which showed that 95+% of the NHI was converted to cyclic siloxazanes. The solution was then heated to reflux again, the remaining TMDSO was added over 10 minutes, and heating of the solution continued to 106.6° C. over at least 35 minutes. The solution was analyzed by GC. The solution was then heated to 110° C. to 115° C. for 1 hour and then cooled. No observable amount of NHI was observed in the GC.

In Comparative Examples 10 and 11, when a hydrosilylation reaction accelerator is used together with a hydrosilylation reaction catalyst, a method for preparing a cyclic siloxazane of the formula -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- is disclosed in U.S. Patent No. 5,026,890 It was shown that higher yields were obtained in a shorter time than a method similar to that disclosed in . This was evidenced by an almost complete conversion to the cyclic siloxazane in Example 11 within 3 hours compared to the sluggish response in Comparative Example 10; Moreover, this was much shorter than the method presented in US Pat. No. 5,026,890, Example 9, in which case the only reaction product identified after 6 hours of reaction after complete addition of TMDSO to the aryl-amine was NHI. Other examples of U.S. Patent No. 5,026,890 provide distilled cyclic siloxazanes in yields up to 95%, while Example 9 of U.S. Patent No. 5,026,890 only provides a theoretical value of 53% for isolated yields. Assuming a 77% isolated yield of cyclic siloxazanes, -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH-, from the process disclosed in this patent, and improved volumetric efficiency without the need to account for extra allyl-amine, the present invention provides This resulted in a 5% to 85% yield improvement over the method in US Pat. No. 5,026,890 with isolated yields of 95% and 53% respectively.

In this Example 12, cyclic -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- was synthesized using allyloxydiphenylsilane as promoter, and an attempt was made to reuse the catalyst. To a 250 mL one-necked flask equipped with a fused glass thermowell was added 23.8742 g of allylamine, followed by 2 mL of Pt-allyloxy-di-(2,4,6-trimethylphenyl)silane catalyst from Reference Example 4 The solution was added and the resulting mixture was heated to reflux. 11.5962 g of TMDSO was added over 1.5 hours. Gas was produced during and after addition. The solution was stirred for 20 minutes and then a GC sample was collected. Another 11.5811 g of TMDSO was added over 2 hours with heating below 72°C. Gas was produced during and after addition. The pot temperature was held at about 70° C. for 1 hour and then cooled to ambient temperature. GC samples were collected.

The reflux condenser was replaced with a 15 cm Vigreux column with a cooled distillation head and a 100 mL receiving flask. The initial portion of allylamine (to be recycled in the next batch) was collected by raising the temperature to 87° C. at ambient pressure. During the collection of allylamine, the temperature was raised to 94°C. The distillation apparatus was then evacuated and sealed to further distill allylamine for reuse. 0.0586 g of (NH ₄ ) ₂ SO ₄ was added to the pot at 87° C., stirred for 10 minutes, and then distillation was resumed with heating under vacuum. The product was collected over 2 hours in 85% yield.

A cooled reflux condenser was attached to the pot, 5.5614 g of allylamine was added and heated to reflux. 5.7376 g of TMDSO were added over 1.5 hours. Gas was produced during and after addition. The solution was heated gradually to 68.2°C. After the addition was complete, the solution was stirred for 10 min and then subsequently cooled to room temperature. GC showed that more cyclic -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- was produced.

This Example 12 shows that the catalyst and promoter can be reused in the process described herein when a phenyl group bonded directly to the silicon atom of the promoter is present. The cyclic -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- produced in a process using an alternative hydrosilylation reaction promoter, allyloxy-dimethylsilane (AMM), is distilled to reuse residual catalyst from the resulting pot residue. The trial was unsuccessful and no further hydrosilylation was observed when combining allylamine and TMDSO with the pot residue. This was confirmed by GC-FID analysis. An important difference was the use of bulk phenyl groups instead of methyl groups on the hydrosilylation promoter, which was believed to impart stability to the catalyst. Without wishing to be bound by theory, it is believed that the use of bulker organic groups bound to the metal catalyst may confer improved thermal stability.

In Comparative Example 13, a cyclic siloxazane of the formula -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- was synthesized using acetoxy-dimethylsilane as a hydrosilylation accelerator. Acetoxy-dimethylsilane was combined with tetramethyldisiloxane and Pt (1,1,3,3-tetramethyl-divinyl-disiloxane complex) at room temperature. After the initial addition of allylamine, a white precipitate was formed and no cyclic -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- was observed according to GC analysis.

In Example 15, cyclic -SiMe ₂ OSiMe ₂ CH ₂ CH(CH ₃ )CH ₂ NH- was synthesized using (1,1-dimethyl)allyloxy-diphenylsilane as a hydrosilylation reaction accelerator. To a 250 mL one-necked flask equipped with a fused glass thermowell was added 5.32 g of 2-methyl-allylamine, followed by the addition of 0.25 g of Pt-(1,1-dimethyl)allyloxy-diphenylsilane catalyst solution. (this will give about 60 ppm Pt and 400 ppm accelerator in the final solution mixture) and the resulting mixture heated to 62°C. 10.05 g of TMDSO was added over 3.5 hours, in which case the temperature was gradually increased to 77°C. Gas was produced during and after addition. The solution temperature was then increased to 80° C., stirred for 1 hour, and then allowed to cool to ambient temperature. The crude product, cyclic -SiMe ₂ OSiMe ₂ CH ₂ CH(CH ₃ )CH ₂ NH-, was analyzed by GC-FID and GC-MS.

The reflux condenser was replaced with a 15 cm Viglux column with a cooled distillation head and a 100 mL receiving flask. The vessel is stripped at 50° C. to remove the low boilers, then 0.07 g (NH ₄ ) ₂ SO ₄ is added to the pot at ambient temperature and the product, cyclic -SiMe ₂ OSiMe ₂ CH ₂ CH(CH ₃ )CH ₂ NH- was distilled under vacuum at 70-115° C. to give 8.66 g (61% yield) in 99+% yield. The product was characterized by GC-FID, GC-MS, ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR.

In this comparative example 16, cyclic -SiMe ₂ OSiMe ₂ CH ₂ CH ₂ CH by combining the starting materials in a similar manner to Example 12 using the isomer 1-amino-but-3-ene instead of 2-methyl-allylamine Attempts were made to synthesize ₂ CH ₂ NH—. To a 250 mL one-necked flask equipped with a fused glass thermowell was added 6.18 g of 1-amino-but-3-ene followed by 0.35 g of Pt-(1,1-dimethyl)allyloxy-diphenylsilane catalyst. The solution was added (this would give about 75 ppm Pt and 500 ppm accelerator in the final solution mixture) and the resulting mixture was heated to about 75°C. 11.67 g of TMDSO was added over 2 hours. Gas was produced during and after addition. The solution temperature was then increased to 80° C., stirred for 2 h, and the product mixture was analyzed by GC-FID and GC-MS, which showed that of the cyclic -SiMe ₂ OSiMe ₂ CH ₂ CH ₂ CH ₂ CH ₂ NH- No evidence of formation was provided.

In this Example 17, cyclic -SiMe 2 OSiMe ₂ CH ₂ CH ₂ CH ₂ NMe- using (1-methyl- ₂ -propin-1-yl)oxy-diphenylsilane (M1PPP) as hydrosilylation promoter was synthesized. 4.92 g of N-methyl-allylamine and 0.087 g of Pt/M1PPP promoter catalyst solution from Example 4g, which gave about 23 ppm Pt and 70 ppm promoter in the final solution mixture, were mixed with a fused glass thermowell and a reflux condenser was added to a 250 mL one-necked flask equipped with The solution was heated to 62.5°C. 9.28 g of TMDSO were added over 3 hours, in which case the temperature was gradually increased to 92°C. Gas was produced during and after addition. The solution temperature was then increased to 80° C., stirred for 1 hour, and then allowed to cool to ambient temperature. The crude product contained cyclic -SiMe ₂ OSiMe ₂ CH ₂ CH ₂ CH ₂ NMe-, which was characterized by GC-FID and GC-MS. Theoretically, this material can be purified by distillation methods.

In this Example 18, cyclic -SiMe ₂ OSiMe ₂ OSiMe ₂ CH ₂ CH ₂ CH ₂ NH- was synthesized using allyloxy-diphenylsilane (APP) as the hydrosilylation promoter. 11.58 g of allylamine and 0.3 g of Pt/APP promoter catalyst solution from Example 4c, which gave about 22 ppm Pt and 65 ppm promoter in the final solution mixture, were mixed in 250 mL 1 with a fused glass thermocouple sheath and reflux condenser. was added to the old flask. The solution was heated to 52.7°C. 41.07 g of 1,1,3,3,5,5-hexamethyltrisiloxane (HMTSO) was added to the reaction mixture over 7.5 hours, in which case the temperature was gradually increased to 82.4°C. The solution was then heated to about 95° C. for 30 minutes and then allowed to cool to about 67° C., which was held for 1.5 hours. Gas was produced during and after addition. The solution temperature was then increased to 80° C., stirred for 1 hour, and then allowed to cool to ambient temperature. The crude product contained cyclic -SiMe ₂ OSiMe ₂ OSiMe ₂ CH ₂ CH ₂ CH ₂ NH-, which was characterized by GC, but only gave low yields (<25%), with most of the material being trisiloxane, HSiMe ₂ OSiMe ₂ OSiMe ₂ H 2 NCH 2 CH 2 CH 2 SiMe-2 OSiMe 2 SiMe 2 CH 2 CH 2 CH 2 NH is converted to the product of allylamine which undergoes a hydrosilylation reaction at both of the SiH moieties on H ₂ NCH ₂ CH ₂ CH ₂ SiMe- ₂ OSiMe ₂ SiMe ₂ CH ₂ CH ₂ CH ₂ NH ₂ was provided. In theory, the cyclic -SiMe ₂ OSiMe ₂ OSiMe ₂ CH ₂ CH ₂ CH ₂ NH- can be purified by distillation methods.

Part II. Preparation of amino-functional polyorganosiloxanes

[Table 2]

The starting materials in Table 2 bearing the brands Dowsil™, Seal-Off™ and SILASTIC™ are commercially available from Dow Silicones Corporation of Midland, Michigan.

In this Example I, a single source of cyclic -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- in MeOH solution was converted to MeO-SiMe ₂ OSiMe ₂ C ₃ H ₆ NH ₂ as follows. In a 250 mL, one-necked flask equipped with a fused glass thermowell, 75.75 g of a crude mixture of about 55% cyclic -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- with the remainder being hydrocarbons and siloxane materials as well as traces of platinum. consists of) was added. A condenser was added to the top of the flask and cooled to about -15°C. About 61.0 mL of methanol was added to the flask over 30 minutes, resulting in a gradual exotherm of 21.3°C. The solution was refluxed at approximately 72° C. for 7 hours.

In this Example II, MeO-SiMe ₂ OSiMe ₂ C ₃ H ₆ NH ₂ was purified by distillation. The condenser on the flask from Example I was replaced with a 15 cm Viglux column, distillation head and receiving flask. The flask was heated to about 115° C. without vacuum to remove excess methanol and other components having a boiling point less than MeO—SiMe ₂ OSiMe ₂ C ₃ H ₆ NH ₂ . MeO-SiMe ₂ OSiMe ₂ C ₃ H ₆ NH ₂ was collected under vacuum from -20 inHg to -28 inHg and heated to about 130°C. A theoretical yield of about 38% of MeO-SiMe ₂ OSiMe ₂ C ₃ H ₆ NH ₂ was collected.

In this Example III, a single source of cyclic -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- in EtOH solution was converted to EtO-SiMe ₂ OSiMe ₂ C ₃ H ₆ NH ₂ . To a 15 mL vial, about 3.0 g of cyclic -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- were added and stirred vigorously. 0.8 g EtOH was added to the vial over 12 minutes. The vial was stirred for 3 days to convert 90+% of the cyclic siloxazane to EtO-SiMe ₂ OSiMe ₂ C ₃ H ₆ NH ₂ .

In this Example IV, multiple sources of cyclic -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- were combined in solution and converted to MeO-SiMe ₂ OSiMe ₂ C ₃ H ₆ NH ₂ . To a 250 mL, one-necked flask equipped with a fused glass thermowell was added 60.0 mL of MeOH. MeOH was heated to reflux and stirred vigorously. Four sources of crude cyclic -SiMe ₂ OSiMe ₂ C ₃ H ₆ NH- containing 30% to 90% of cyclic siloxazanes of mass 15.7 g, 16.0 g, 16.2 g and 16.6 g were added to the flask over 6 hours. did. In each case, the solution became discolored. Samples were analyzed by GC between each addition, showing that approximately the same impurity was produced after each addition. After the final addition, the resulting solution was stirred at about 72° C. for 3 hours to prepare a mixture in which the largest component by mass, not methanol, was MeO-SiMe ₂ OSiMe ₂ C ₃ H ₆ NH ₂ .

In this Example V, a terminal amino-functional siloxane was synthesized via a condensation reaction using MeO-SiMe ₂ OSiMe ₂ C ₃ H ₆ NH ₂ . A 250 mL three-necked round bottom flask was charged with the following materials: a silanol end-blocked polydimethylsiloxane (148.7 g) having a viscosity of 70 mPa·s at 25° C. measured according to the following test method, and MeO-SiMe ₂ OSiMe ₂ C ₃ H ₆ NH ₂ (1.78 to 2 g). The resulting mixture was heated to 90° C. under a nitrogen sweep for 10 minutes. After 10 min, propionic acid (0.76 g to 1.02 g) was added and the resulting mixture was stirred at 90° C. for 2 to 3 h. A distillation vacuum was then applied at a pressure of less than 20 mmHg for 210 minutes to allow forward reaction as indicated by the increase in viscosity over time. The excess propionic acid was then removed by stripping in a temperature range of 100° C. to 150° C. depending on vacuum pressure and stripping time. Upon completion, the resulting fluid was cooled to room temperature and purged with nitrogen prior to storage. This fluid appeared clear and colorless and was an amino-functional polydimethylsiloxane copolymer with dimethyl-propylamine end caps. The copolymer had a viscosity of 2500 mPa·s to 4000 mPa·s at 25° C. measured according to the following test method, and a transmittance to water of 100%. The copolymer was stable for 4 months after aging at 45° C. as evidenced by no detectable ammonia odor after aging.

In this Example VI, bis-aminopropyl polydimethylsiloxane having a Mw of 1,400 g/mol and a DP of 16 was synthesized as follows. Into a 250 mL three neck round bottom flask equipped with a thermocouple, magnetic stir bar, and condenser with a gas adapter, about 100 g (0.1 mol) of bis-silanol-terminated polydimethylsiloxane (average Mw 1,000 g/ mol) (OH-PDMS 2) was added. The flask was continuously purged with N ₂ and the OH-PDMS 2 was stirred vigorously. The flask was then heated to about 64° C. with 39.16 g (0.207 mol) of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane (cyclic-SiMe ₂ OSiMe ₂ C ₃ H ₆ NH-) was added over 10 min. The reaction mixture in the flask was heated to a maximum temperature of about 74° C. and then cooled down. The reaction mixture was maintained at 75° C. by increasing the heat applied and stirred for 30 minutes. The heating was then stopped and the reaction mixture was allowed to cool to room temperature and stirred overnight while flushing the headspace with nitrogen. The composition was confirmed by ¹ H NMR and ²⁹ Si NMR, and the liquid had a viscosity of 8 mPa·s to 10 mPa·s.

In this Example VII, bis-aminopropyl polydimethylsiloxane having a Mw of 3,500 g/mol and a DP of 44 was synthesized at room temperature as follows. A 250 mL three neck round bottom flask equipped with a thermocouple, magnetic stir bar, condenser with gas adapter, and in situ (in-situ) of the reaction by observing the disappearance of vibrations (measured at 894 cm ⁻¹ ) consistent with Si—OH. A device comprising a diamond tip ReactIR (ReactIR) for in situ monitoring was provided. To the flask was added about 104.63 g (33.8 mmol) of bis-silanol-terminated polydimethylsiloxane (OH-PDMS 3) having an average Mw=3,100 g/mol. The flask was inactivated with N ₂ and OH-PDMS 3 was stirred vigorously. The room temperature of OH-PDMS 3 was measured to be 23.4°C. 13.88 g (73.4 mmol) of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane were added over 1 min. The reaction between these starting materials temporarily raised the pot temperature to 29.2° C. over 6 minutes and then subsequently returned back to room temperature. According to the observation, it was demonstrated that the reaction was effectively completed after 6 hours, and ¹ H NMR and ²⁹ Si NMR spectra confirmed this.

In this Reference Example VIII, the general procedure for preparing the terminal bis-aminopropyl-terminated polydimethylsiloxane was carried out as follows.

A 20 mL vial was charged with the following starting materials: bis-silanol-terminated polydimethylsiloxane and 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-di Silacycloheptane. The resulting mixture was mixed at reaction temperature until homogeneous. The resulting product was a bis-aminopropyl-terminated polydimethylsiloxane. The reaction progress was monitored using ²⁹ Si-NMR and FTIR. The polymer was stable for 6 months after aging at 45°C. Selection and amount of bis-hydroxy-terminated polydimethylsiloxane (silanol), 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane (terminated capping agent), reaction conditions, and results are shown in Table X below.

[Table X]

In this Reference Example IX, a general procedure for preparing a terminal bis-aminopropyl-terminated polydimethylsiloxane through a condensation reaction was performed as follows.

A 250 mL three neck round bottom flask was charged with the following materials: bis-silanol-terminated polydimethylsiloxane (silanol) having a viscosity of 70 mPa·s and 1,1,3,3-tetramethyl -2-oxa-7-aza-1,3-disilacycloheptane (endcapping agent). The resulting mixture was heated to 90° C. for 10 minutes under a nitrogen sweep. After 10 min propionic acid was added and the resulting mixture was stirred at 90° C. for 2 h. A distillation vacuum was then applied at a pressure of less than 20 mmHg for 3.5 hours to allow forward reaction as indicated by the increase in viscosity over time. Excess propionic acid was removed by stripping in a temperature range of 100° C. to 150° C. depending on vacuum pressure and stripping time. Upon completion, the resulting product was cooled to room temperature and purged with nitrogen prior to storage. The resulting product was a clear, colorless fluid and appeared to be a bis-aminopropyl-terminated polydimethylsiloxane.

[Table XI]

In this Example X, polyorganosiloxanes having both terminal and pendant amino-functional groups were prepared as follows. A 250 mL three-necked round bottom flask was charged with the following starting materials: bis-silanol-terminated polydimethylsiloxane (silanol) having a viscosity of 70 mPa·s (97.1% by weight), 3-aminopropyl diethoxysilane (1.3 wt%), and 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane (endcapping agent) (1 wt%). The resulting mixture was heated to 90° C. for 10 minutes under a nitrogen sweep. After 10 min propionic acid (0.6 wt %) was added and the resulting mixture was stirred at 90° C. for 2 h. A distillation vacuum was then applied at a pressure of less than 20 mmHg for 3.5 to 4 hours to allow forward reaction as indicated by the increase in viscosity over time. Excess propionic acid was removed by stripping in a temperature range of 100° C. to 150° C. depending on vacuum pressure and stripping time. Upon completion, the product was cooled to room temperature and purged with nitrogen prior to storage. The resulting clear, colorless fluid was an aminopropyl-terminated, aminopropyl-functional polydimethylsiloxane copolymer having a final viscosity of 1800 mPa·s to 2200 mPa·s.

In this Example XI, 1,3-bis(3-aminopropyl)-1,3-dimethyl-1,3-diphenyldisiloxane was synthesized as follows. A 250 mL three neck round bottom flask was charged with 21.52 g of phenyl-methylsiloxane containing mainly 1,3-dimethyl-1,3-diphenyl-disiloxane-1,3-diol. It was heated to 90° C. under a nitrogen sweep with mixing. When 90° C. was reached, the flask was charged with 53.27 g of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane. The mixture was stirred at 300 rpm at 90° C. for 7 hours. The reaction was monitored by proton NMR and SiOH consumption was monitored by ²⁹ Si NMR.

In this Example XII, the ammonia concentration in the sample prepared according to Reference Example VIII above was analyzed as follows. The bis-aminopropyl-terminated polydimethylsiloxane prepared according to Reference Example VIII was aged in an oven at 45° C. or at room temperature for 6 months. A Hydrion™ CAT#AM-40 paper was used to quantify the concentration of ammonia gas present in the headspace of the vessel for each sample. The final NH ₃ concentration was highly dependent on the amount of excess 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane added to the reaction, with higher amounts being more pronounced It was found to lead to an NH ₃ odor. Sample preparation conditions and aging conditions for the bis-aminopropyl-terminated polydimethylsiloxane product are shown in the table below.

[graph]

In this Example XIII, the viscosity stability of the samples prepared according to Reference Example VIII above was analyzed as follows: Bis-aminopropyl-terminated polydimethylsiloxane prepared according to Reference Example VIII was subjected to 45° C. oven or room temperature. aged for 6 months in Viscosity before and after aging was measured as described below. The results are shown in the table below. The viscosity of the bis-aminopropyl-terminated polydimethylsiloxane remained stable over the course of 6 months at ambient temperature and elevated temperature (45° C.).

In this Example XIV, the terminal amino-functional polydiorganosiloxane prepared as described above can be assayed for reduction of hair friction by conditioning the hair as follows. Preparation of Hair Conditioner Formulation (Processing) In a rinse conditioning formulation using an amount sufficient to provide 1% polydiorganosiloxane with terminal amino-functional groups, terminal amino-functional groups (TAS) and 2000-2700 mPa ·s and a polydiorganosiloxane having a viscosity of 13,000 to 16,000 mPa·s will be added. Conditioning formulations are shown in the table below. Conditioning formulations will be prepared using TAS (2000-2700 mPa·s). Dowcil™ 2-8566 Amino Fluid and Pantene Smooth & Sleek will be used as comparative studies.

[Table I]

1. CELLOSIZE™ PCG-10 available from Dow Chemical

2. VERSENE™ 220 available from Dow Chemical

3. Crodacol™ CS50 available from Croda

4. Arlacel™ 165 available from Croda

5. Control does not contain silicone block copolymer

6. NEOLONE™ PE available from Dow Chemical

7. Dousil™ 2-8566 Amino Fluid

Lower number = lower friction = smoother hair surface = better results. 1% Si in rinse-in conditioner applications

Deionized water was added to the mixing vessel and heated to 70°C. With moderate stirring, the hydroxyethyl cellulose was dispersed until completely dissolved. Heat was reduced to 60° C. and cetearyl alcohol and PEG-100 stearate and glyceryl stearate and silicone block copolymer (if present) were added. The conditioner was mixed for 3 minutes, then tetrasodium EDTA was added and mixed for 3 minutes. When the temperature was below 40°C, phenoxyethanol and methylisothiazolinone were added. The water loss was compensated and the resulting formulation was mixed for an additional 5 minutes. The final pH of all conditioner formulations was approximately 5.

Medium bleached European hair from International Hair Importers was used to test the conditioning formulations prepared in the present invention. Each tress weighed 2 grams. Each tress was rinsed for 15 seconds under a flow of tap water at 40°C. Using a pipette, 0.4 g of a solution containing 9% sodium lauryl sulfate was applied and bubbled through a tress for 30 seconds. The tress was rinsed under running water for 30 seconds. Excess water was removed from the tress by passing the tress between the index and middle fingers of the hand. The tresses were placed on a tray covered with paper towels and dried overnight. Each tress was hand-combed three times using the narrow teeth of an ACE™ comb and evaluated using the INSTRON WET COMBING and INSTRON DRY COMBING procedures. The Instron procedure is a standard, accepted, and industry-accepted protocol, and is described, for example, in US Pat. Nos. 5,389,364 (February 14, 1995), 5,409,695 (April 25, 1995), 5,419,627 (1995). May 30, 1996), and 5,504,149 (April 2, 1996).

For condition related tests, the hair tresses were rinsed with tap water at 40° C. for 30 seconds. The test conditioner was applied to the tress in an amount of 0.8 g, and the tress was stroked for 30 seconds. The tress was rinsed under tap water at 40° C. for 30 seconds. Excess water was removed by pulling the tress through the index and middle fingers of the hand. The tresses were allowed to dry separately on paper towels overnight at room temperature. The tresses were combed once prior to performing the Instron study.

Instron combing was used to determine conditioning performance by wet combing and dry combing. This test uses an Instron strain gauge, which is set up to measure the force required to comb the hair. Conditioning performance was based on the ability of a particular hair treatment formulation, such as a shampoo or hair conditioner, to reduce the force required to comb the hair, using an Instron strain gauge. This force was recorded as Average Combing Load (ACL). The lower the number of ACL values, the better the conditioning effect conferred by the formulation tested.

According to the Instron dry combing method, the hair was untangled by combing the tress 3 times. The hair was then re-tangled by turning the tress three times clockwise and then three turns counterclockwise. The tress was then placed on a hanger and Instron combing was performed. Re-tangling and Instron combing were repeated until all data points were collected. For each treatment, the average combing force for three tresses was measured.

According to the Instron wet combing method, the hair was first wetted by dipping it into distilled water and then detangled by combing the tress three times. The tress was then re-entangled by dipping three times in distilled water. Excess water was removed by passing the tress twice with the index and middle fingers of the hand. The tress was placed on a hanger and an Instron comb was performed. The retangling and Instron combing steps were repeated until all data points were collected. For each treatment, the average combing force for three tresses was measured.

[Table III]

The coefficient of friction is an industry standard method for measuring the reduced friction properties of a treatment to hair and correlates with sensory attributes for smoothness and softness. A Diastron MTT175 tensile tester with a normal force of 50 g mounted on a rubber probe was used for testing in a constant temperature and humidity chamber. Three tresses per treatment and five measurements per tress were tested to generate friction data with and against hair cuticles. The coefficient of friction (COF) is F/N, where F is the externally applied force and N is the normal force. The same tress from the combing study was used to measure the coefficient of friction in the dry state.

The results showed that the rinse-on conditioning formulation containing TAS prepared according to the present invention provided an improvement in friction reduction compared to the control conditioner, Dowsil™ 2-8566 and Pantine Smooth & Slick.

[graph]

[graph]

In this Example XV, 457 g of about 120,000 g/mol silanol terminated polydimethylsiloxane fluid (viscosity of about 341,000 mPa·s) was preheated to 145° C. followed by 1 L 3 spheres with an overhead sweep of nitrogen. Bis-aminopropyl polydimethylsiloxane with Mw = 120,500 g/mol and DP = 1627 was synthesized by stirring using a mechanical stirrer in a flask. 1.60 g of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane was added to the silanol terminated polydimethylsiloxane fluid followed by stirring for 8 hours did. Stirring was stopped, the fluid was allowed to cool to ambient temperature and the product was collected. Silanol was shown to be effectively capped to give 3-aminopropyl-terminated polydimethylsiloxane, which was characterized using ²⁹ Si NMR with cyclodimethyltrisiloxane internal standard. The viscosity of the product was measured to be about 358,000 mPa·s.

In this Example XVI, the number average molecular weight measured by GPC in a DAC 500 FVZ SpeedMixer™ cup under a nitrogen atmosphere is 340,000 and the weight average molecular weight is 650,000 and the plasticity value according to the method described below is within 55 to 65 99.84 g of phosphorus hydroxyl terminated polydimethylsiloxane HO-(Si(CH ₃ ) ₂ O) _n -Si-OH, purchased from Dow Silicones Corporation under the trade designation XIAMETER™ RBG-0910 gum possible) and 0.17 g of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane, bis-amino having a viscosity of 20 to 40 MM mPa·s Propyl polydimethylsiloxane was prepared and mixed 5 times (2350 rpm each time) for 30 seconds. The contents were allowed to cool for 15 minutes between mixing. After mixing, the contents were placed in a 70° C. oven for 12 hours. Viscosity and plasticity values were similar to the original silanol terminated polydimethylsiloxane. Approximately 25% conversion to propylamine terminated polydimethylsiloxane was confirmed by diffusion ²⁹ Si NMR.

In this Example XVII, the general procedure for preparing bis-(3-amino-2-methyl)propyl-terminated polydimethylsiloxane having an average viscosity of 60 mPa·s to 80 mPa·s and a DP=44 was followed. It was provided as follows. Assemble an apparatus comprising a 250 mL three-necked round bottom flask equipped with a condenser with thermocouple, magnetic stir bar, and gas adapter, and approximately 50.05 g with a viscosity of 60 mPa·s to 80 mPa·s (and DP = 40) (16.9 mmol) of bis-silanol-terminated polydimethylsiloxane was added to the flask. The flask was inactivated with N ₂ and the bis-silanol terminated polydimethylsiloxane was stirred vigorously and heated to 90°C. 6.95 g (34.2 mmol) of the product from Example 15 in Part I of this specification, 1,1,3,3,5-pentamethyl-2-oxa-7-aza-1,3-disilacycloheptane ( endcapping agent) was added to the bis-silanol terminated polydimethylsiloxane. The reaction between these starting materials temporarily raised the pot temperature to 92°C over 3 minutes and then subsequently set back to 90°C. The mixture was stirred for 6 h and then cooled to room temperature. The product, bis-(3-amino-2-methyl)propyl-terminated polydimethylsiloxane, showed a DP of 44 based on analysis of ²⁹ Si NMR, and the measured viscosity was between 60 mPa·s and 80 mPa·s. The structure was confirmed using ¹ H NMR, ¹³ C NMR and ²⁹ Si NMR.

In this Example XVIII, 3-(aminopropyl)-1,1,3,3-tetramethyl disiloxy terminated MQ resin was synthesized as follows. A 1,000 mL three neck round bottom flask was charged with the following materials: 148.25 g MQ 1 resin solution and 45.05 g HPLC grade xylene. This mixture was stirred using a PTFE stirring paddle attached to a glass stirring shaft rotating at 300 rpm. To the addition funnel, 38.09 g of cyclic siloxazane was charged and added dropwise to the stirred solution over the course of 20 minutes, accompanied by an increase in exothermic temperature of +12.2°C (19.6°C → 31.8°C). The addition funnel was rinsed with 25 mL of HPLC grade xylene. The reaction mixture was heated to 80° C. and maintained at this temperature with stirring for 2 hours. Once cooled, 5.28 g 2-propanol and 20.10 g deionized water were added. A Dean-Stark trap was attached to the reactor with a water-cooled reflux condenser. The reaction mixture was heated (145° C.) for 20 minutes to vigorously reflux the xylene as water and 2-propanol were collected. After cooling to room temperature under a nitrogen blanket, the reaction was transferred to a 2 L rotary evaporator flask and stripped at 5 mmHg for 30 minutes at 120°C.

The resulting reaction product was analyzed by NMR as follows. 9.24 g of reaction product, 0.1941 g of 1,4-dioxane (internal standard), and 13.8670 g d -chloroform containing Cr(acac) ₃ at a concentration of 0.04 M were combined in a PTFE NMR tube, ²⁹ Si and ¹³ Subjected to both C NMR, an average composition of M ^Me3+NH2 _0.432 D ^Me2 _0.109 (Q _0.459 )OH _0.023 (where subscripts indicate mole fraction) and an amine hydrogen equivalent of 545.8 g/mol NH on a solids basis was revealed. lost.

In this Example XIX, 3-(aminopropyl)-1,1,3,3-tetramethyl disiloxy terminated T-phenyl resin was synthesized as follows. A 1,000 mL three neck round bottom flask was charged with the following starting materials: 100.04 g of hydroxyl-functional polyphenylsilsesquioxane (commercially available as Dousyl™ 217 resin) and 64.15 g of HPLC grade xylene. This mixture was stirred using a PTFE stirring paddle attached to a glass stirring shaft rotating at 300 rpm. The reaction mixture was heated to 50 °C. 37.39 g of cyclic siloxazane was added dropwise to the stirred solution over the course of 3 minutes, resulting in an exothermic temperature increase of +18.3° C. (52.7° C. → 71.0° C.). The addition funnel was rinsed with 20 mL of HPLC grade xylene and charged with 23.66 g of hexamethyldisilazane (commercially available as Dousil™ Z-6079 fluid). Hexamethyldisilazane (HMDZ) was added over the course of 2 minutes, and no increase in exothermic temperature was observed. The solution was heated to 80° C. and held at this temperature for 4 hours. After cooling, 20.07 g of HPLC grade 2-propanol and 5.03 g of deionized water were added to quench any unreacted silazanes and/or siloxazanes. A Dean-Stark trap was attached to the reactor with a water-cooled reflux condenser. The reaction mixture was heated (145° C.) for 30 minutes to vigorously reflux the xylene as water and 2-propanol were collected. After cooling to room temperature under a nitrogen blanket, the reaction was transferred to a 2 L rotary evaporator flask and stripped at 5 mmHg at 120°C. To redisperse the product, 23.96 g of HPLC grade xylene was added to create an 85% solution.

4.0977 g of reaction product, 0.1136 g of 1,4-dioxane (internal standard) and 5.7538 g d -chloroform containing Cr(acac) ₃ at a concentration of 0.04 M were combined in a PTFE NMR tube, ²⁹ Si and ¹³ C Subjecting to both ^{NMRs revealed an average composition of M Me3+NH2} _0.221 D _0.146 (T ^Ph _0.634 )OH _0.027 and an amine hydrogen equivalent of 326.3 g/mol NH on a solids basis.

In this Example XX, 1,1,1-triethyl-3,3,5,5-tetramethyl-5-(3-aminopropyl)-trisiloxane was synthesized as follows, 1.0218 g (5.39 mmol) of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane was added to an about 8 mL vial equipped with a stir bar and mixed at ambient temperature. 0.7136 g (6.14 mmol) of triethylsilanol was added to the vial and the flask was stirred over 15 minutes exothermic to at least about 37°C. After the flask was cooled over 15 min, the product was analyzed by GC-FID, GC-MS and ¹ H and ¹³ C NMR, which converted 90+% of the cyclic siloxazane, with the main product being Et ₃ SiOSiMe ₂ OSiMe ₂ C ₃ H ₆ NH ₂ .

In this Example XXI, 1,1,1-triisopropyl-3,3,5,5-tetramethyl-5-(3-aminopropyl)-trisiloxane was synthesized as follows, 0.9770 g (5.16 mmol) ) of 1,1,3,3-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane was added to an about 8 mL vial equipped with a stir bar and mixed at ambient temperature. 0.9030 g (5.16 mmol) of tri-isopropylsilanol was added to the vial and stirred for 16 days, showing that 90+% was converted to iPr ₃ SiOSiMe ₂ OSiMe ₂ C ₃ H ₆ NH ₂ . The product was analyzed by GC-FID, GC-MS and ¹ H and ¹³ C NMR.

Example W above showed that cyclic siloxazanes can be efficiently prepared by the methods described herein. Cyclic siloxazanes can be used as capping agents for silanol-functional organosilicon compounds, including silanol-functional polyorganosiloxanes, such as silanol-terminated polydiorganosiloxanes. Polydiorganosiloxanes having terminal amino-functional groups can be prepared, such polydiorganosiloxanes being prepared, for example, as aminopropyl-terminated polydimethylsiloxanes prepared as described herein at room temperature and 45°C. The viscosity of the aminopropyl-terminated polydimethylsiloxane prepared as described herein, and Example XII described above, showing that it had low ammonia concentrations after aging at both °C, aged at both room temperature and 45 °C. have improved stability compared to amino-functional siloxanes prepared by conventional methods (eg, as disclosed in US Pat. No. 7,238,768), as demonstrated by Example XIII, which shows that can

Definitions and Usage of Terms

Unless otherwise indicated by the context of this specification, all amounts, ratios and percentages herein are by weight; the articles 'a', 'an', and 'the' each refer to one or more; The singular includes the plural. The content and abstract of the invention are incorporated herein by reference. The conjunctions "comprising", "consisting essentially of, and "consisting of are in the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018 at section §2111.03 I., II., and III. used as described. The use of “for example,” “such as,” “such as,” and “including” to enumerate illustrative examples is not limited to the recited examples only. Thus, “for example” or “such as” means “eg, but not limited to,” or “such as, but not limited to,” and encompasses other similar or equivalent examples. Abbreviations used herein have the definitions in Table 8.

[Table 8]

The following test methods were used to determine the properties of the starting materials herein.

Bis-hydroxyl-terminated polydiorganosiloxanes for each polydiorganosiloxane [eg, starting material D-II) having a viscosity of 250,000 mPa·s or less and/or amino-functional polys prepared therewith diorganosiloxane] was measured at 0.1-50 rpm on a Brookfield DV-III cone & plate viscometer with a #CP-52 spindle. One of ordinary skill in the art will recognize that rotational speed decreases with increasing viscosity, and will be able to select an appropriate rotational speed when using this test method to measure viscosity.

The Williams plasticity number of any polyorganosiloxane considered a gum may be determined by the American Society for Testing and Materials (ASTM) test method 926D as described in US Pat. No. 8,877,293 B2.

²⁹ Si NMR and ¹³ C NMR spectroscopy can be used to quantify hydrocarbon groups (eg, R groups, such as R ⁸ and/or R ⁹ as described above) in the polydiorganosiloxane. ²⁹ Si NMR spectra are described in Taylor et. al. in Chapter 12 of The Analytical Chemistry of Silicones, ed. A. Lee Smith , Vol. 112 in Chemical Analysis, John Wiley & Sons, Inc. (1991), pages 347-417, and section 5.5.3.1]. In Chapter 12, the authors discuss the general parameters inherent in acquiring quantitative NMR spectra from silicon nuclei. Each NMR spectrometer is different with respect to electronics, capabilities, sensitivity, frequency and operating procedure. To adjust, shimming, and calibrate pulse sequences sufficient for quantitative 1D measurements of ²⁹ Si and ¹³ C nuclei in a sample, reference should be made to the instrument manual for the spectrometer to be used.

The main result of NMR analysis is the NMR spectrum. In the absence of a standard, it is recommended that the signal-to-noise ratio of signal height to average reference noise be at least 10:1, which is considered quantitative. Properly acquired and processed NMR spectra result in a signal that can be integrated using any commercially available NMR processing software package.

From this integration, the weight percent of the total R group content can be calculated from the ²⁹ Si NMR spectrum according to: (I ^M ) - (U ^M ) = G ^M ; (I ^M(R) ) - (U ^M(R') ) = G ^M(R) ; (I ^D ) - (U ^D ) = G ^D ; (I ^D(R) ) - (U ^D(R) ) = G ^D(R) ; U ^R / U ^M(R) = Y ^R' ; U ^R / U ^D(R) = Y ^R";

Y ^{R ''} - [G ^M(R) / (G ^M + G ^M(R) + G ^D + G ^{D (R)} ) - 100] = W ^{R ';}

Y ^{R '"} - [G ^{D (R)} / (G ^M + G ^M(R) + G ^D + G ^{D (R)} ) - 100] = W ^{R "} ; and W ^{R '} + W ^{R "} = total W ^R ;

where I is the integration signal of the indicated siloxy group; U is the unit molecular weight of the indicated siloxy group; G is a placeholder for gram units; W is the weight percent of the indicated siloxy units; Y is the ratio value for the specified siloxy units; R is as described above; R' only represents the R group from M(R); R″ only represents the R group from the D(R) group.

- 1H-NMR and ¹⁹⁵ Pt NMR were evaluated using the following instruments and solvents: A Varian 400 MHz mercury spectrometer is used. C6D6 is used as solvent.

- Gas chromatography-flame ionization detector (GC-FID) conditions: a capillary column with a length of 30 meters and an inner diameter of 0.32 mm, containing a 0.25 μm thick stationary phase in the form of a coating on the inner surface of the capillary column, The stationary phase in this case consisted of phenyl methyl siloxane. The carrier gas was helium gas used at a flow rate of 105 mL/min. The GC instrument is an Agilent model 7890A gas chromatograph. The inlet temperature is 200°C. The GC experimental temperature profile consists of soaking (holding) at 50°C for 2 minutes, ramping the temperature to 250°C at a rate of 15°C/min, and then immersing (holding) at 250°C for 10 minutes.

- GC-MS instruments and conditions: samples are analyzed by electron impact ionization and chemical ionization gas chromatography-mass spectrometry (EI GC-MS and CI GC-MS). Agilent 6890 GC conditions were DB-1 column with 30 meter (m) x 0.25 millimeter (mm) x 0.50 micrometer (μm) film configuration, inlet temperature of 200 °C, immersion at 50 °C for 2 min, 15 °C/min. It includes an oven program of ramping to 250° C., and immersion at 250° C. for 10 minutes. Helium carrier gas flowing at a constant flow of 1 mL/min and a 50:1 split injection. Agilent 5973 MSD conditions include MS scans ranging from 15 to 800 Daltons, EI ionization, and CI ionization using a custom CI gas mix of 5% NH ₃ and 95% CH ₄ .

Polyorganosiloxane starting materials (eg, starting material D described herein), and amino-functional polyorganosiloxanes by GPC according to the test method of Reference Example 1 at column 31, US Pat. No. 9,593,209, column 31 can measure the number average molecular weight of The transmittance of the amino-functional polydimethylsiloxane prepared in the preceding examples was measured against water using a Spectronic 21: Milton Roy.

It is to be understood that the present invention has been described in an exemplary manner, and that the terminology used is intended to be descriptive rather than limiting in its wording. With respect to any Markush group required herein for the description of a particular feature or aspect, different, special, and/or unexpected results from each member of the individual Markush group may result from all other Markush groups. Can be obtained independently of Kush members. Each member of the Markush group may be required individually and/or in combination, providing adequate support for specific embodiments within the scope of the appended claims.

Moreover, any ranges and subranges required for describing the present invention are independently and collectively intended to fall within the scope of the appended claims, and all ranges (including integer and/or fractional values within said ranges) are intended to It is understood that such values are described and contemplated, even if not explicitly recited herein. Those of ordinary skill in the art will appreciate that the recited ranges and subranges fully describe and enable various embodiments of the invention, and such ranges and subranges may be further subdivided into related halves, 1/3, 1/4, 1/5, etc. easily recognize that By way of example only, the range of “1 to 18” is further subdivided into a lower third, i.e., 1 to 6, a middle third, i.e., 7 to 12, and an upper third, i.e., 13 to 18. may be made, which are individually and collectively within the scope of the appended claims, and are individually and/or collectively required and provide adequate support for specific embodiments within the scope of the appended claims. can do. Also, with respect to language limiting or modifying ranges, e.g., "greater than", "greater than", "less than", "less than", etc., such language should be understood to include subranges and/or upper or lower limits. .

Claims (35)

A method for preparing a cyclic polysiloxazane, comprising:
One)
a) allyl-functional amines;
b) a platinum catalyst capable of catalyzing the hydrosilylation reaction, and
c) chemical formula

Hydrosilylation reaction accelerator of (here,

represents a bond selected from the group consisting of a double bond and a triple bond, the subscript a is 1 or 2, and the subscript b is 0 or 1, provided that

is a double bond, then a = 2 and b = 1,

a = 1 and b = 0 when is a triple bond; each R ¹ is independently selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ² is selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ³ is selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ⁴ is selected from the group consisting of hydrogen, an alkyl group of 1 to 15 carbon atoms, and an aryl group of 6 to 20 carbon atoms; R ⁵ is an independently selected monovalent hydrocarbon group of 1 to 15 carbon atoms; R ⁶ is an independently selected monovalent hydrocarbon group of 1 to 15 carbon atoms;
forming a reaction mixture, and then
2) to the reaction mixture,
d) chemical formula

by adding a SiH ^- terminated siloxane oligomer of Step of preparing polysiloxazane
A method comprising The method according to claim 1 , wherein the starting material a), the allyl-functional amine has the formula:

(wherein each R ⁹ is independently selected from the group consisting of hydrogen and an alkyl group of 1 to 15 carbon atoms). 3. The method of claim 2, wherein the allyl-functional amine is selected from the group consisting of 2-methyl-allylamine and allylamine. 4. The complex according to any one of claims 1 to 3, wherein the starting material b), the hydrosilylation reaction catalyst is i) a platinum metal, ii) a compound of platinum, iii) a complex of the compound of platinum with a low molecular weight organopolysiloxane , iv) said compound of platinum microencapsulated in a matrix or core-shell type structure, v) said complex of said compound of platinum microencapsulated in a matrix or core-shell type structure, and vi) combinations of two or more thereof. chosen way. 5. The method according to any one of claims 1 to 4, wherein the starting material c), the accelerator

(1,1,-dimethyl-2-propenyl)oxydiphenylsilane,

(1-methyl-2-propenyl) oxydiphenylsilane,

,

,

,

,

,

,

, and

Selected from the group consisting of, the method. 6 . The starting material d) according to claim 1 , wherein the SiH-terminated siloxane oligomer is 1,1,3,3-tetramethyldisiloxane and 1,1,3,3,5 , 5-hexamethyltrisiloxane is selected from the group consisting of. 7. The method of claim 6, wherein the SiH-terminated siloxane oligomer is 1,1,3,3-tetramethyldisiloxane and the cyclic polysiloxazane has the general formula

wherein each R ⁹ is independently selected from the group consisting of hydrogen and an alkyl group of 1 to 15 carbon atoms carbon atoms. The method of claim 7, wherein the cyclic polysiloxazane is

and

Selected from the group consisting of, the method. 7. The method of claim 6, wherein the SiH-terminated siloxane oligomer is 1,1,3,3,5,5-hexamethyltrisiloxane and the cyclic polysiloxazane has the general formula

wherein each R ⁹ is independently selected from the group consisting of hydrogen and an alkyl group of 1 to 15 carbon atoms. 10 . The process according to claim 1 , wherein the starting material e), solvent are added during and/or after step 1). 11. The method according to any one of claims 1 to 10, wherein the combining in step 1) comprises mixing the starting material a), the starting material b) and the starting material c); by heating the reaction mixture to a temperature of 110° C. or less. 11 . The hydrosilylation reaction according to claim 1 , wherein, prior to combining the starting material a), the allyl-functional amine, the starting material b), the platinum catalyst, and the starting material c), the hydrosilylation reaction. A method of combining an accelerator. 13. The method according to any one of claims 1 to 12, wherein step 2) is performed at 20 °C to 200 °C; alternatively 40° C. to 150° C.; alternatively at a temperature of 50°C to 140°C. A process for preparing an amino-functional organosilicon compound comprising:
Preliminary-1) by carrying out the method of any one of claims 1 to 13, comprising the steps of: A) preparing a cyclic polysiloxazane;
One)
A) the cyclic polysiloxazane, and
D) combining starting materials comprising a silanol-functional organosilicon compound to prepare a reaction product comprising the amino-functional organosilicon compound;
optionally, 2) recovering the amino-functional organosilicon compound; and
Optionally, before step 2), adding E) an acid procatalyst to the reaction mixture
A method comprising 15. The method according to claim 14, wherein the starting material D) is a silanol-functional polydiorganosiloxane of the formula:

(wherein R ¹¹ is selected from the group consisting of OH and R ⁸ , and the subscript y has a viscosity measured at 25° C. from 8 mPa·s to 100,000,000 mPa·s; alternatively from 8 mPa·s to 40,000,000 mPa·s; s; alternatively from 70 mPa·s to 500,000 mPa·s; alternatively having a value sufficient to provide the silanol-functional polydiorganosiloxane from 70 mPa·s to 16,000 mPa·s). 16. The method according to claim 14 or 15, wherein step 1) is carried out by mixing at ambient temperature to 150°C. 17. The method according to any one of claims 14 to 16, wherein one of the starting materials A) and D) is continuously or incrementally introduced into a vessel containing the other of the starting materials A) and D). How to add. A process for preparing an α-alkoxy-ω-amino-functional polysiloxane comprising:
I)
A) a cyclic polysiloxazane prepared by the method of any one of claims 1 to 13, and
B) combining starting materials comprising an alcohol of formula R ¹⁰ OH, wherein R ¹⁰ is an alkyl group of 1 to 8 carbon atoms,
C) chemical formula

preparing a reaction product comprising the α-alkoxy-ω-amino-functional polysiloxane of and
Optionally, II) purifying the reaction product C) recovering the α-alkoxy-ω-amino-functional polysiloxane
A method comprising The method of claim 18 , wherein each R ⁸ is an alkyl group and each R ⁹ is hydrogen. 20. Process according to claim 18 or 19, starting material B), wherein the alcohol is selected from the group consisting of methanol and ethanol. A process for preparing an amino-functional organosilicon compound comprising:
Preliminary-1) carrying out the method of any one of claims 18 to 20 to prepare the reaction product formed in step I) and/or purified C) polysiloxazane in step II);
One)
said reaction product and/or C) said polysiloxazane; and
D) combining starting materials comprising a silanol-functional organosilicon compound to prepare a reaction mixture;
Optionally, 2) heating the reaction mixture to 150° C. or less; and
optionally, 3) adding E) acid procatalyst to the reaction mixture after step 1) and before step 2) if step 2) is present.
A method comprising 22. The method according to claim 21, wherein the starting material D) comprises a silanol-functional polydiorganosiloxane of the formula:

(wherein R ¹¹ is selected from the group consisting of OH and R ⁸ , and the subscript y has a viscosity measured at 25° C. from 8 mPa·s to 100,000,000 mPa·s; alternatively from 8 mPa·s to 40,000,000 mPa·s; s; alternatively from 70 mPa·s to 500,000 mPa·s; alternatively having a value sufficient to provide the silanol-functional polydiorganosiloxane from 70 mPa·s to 16,000 mPa·s). 23. The method of claim 15 or 22, wherein the amino-functional organosilicon compound has the formula

is a primary amino group-terminated polydiorganosiloxane of wherein R ¹² is selected from the group consisting of OH, R ⁸ and —CH ₂ CH(R ⁹ )CH ₂ NH ₂ , and the subscript n = (x + y + 1). 24. The method according to any one of claims 14 to 17 and 21 to 23,
In step 1) F) adding an aminoalkyl-functional alkoxysilane to prepare said primary amino group-terminated polyorganosiloxane further comprising pendant aminoalkyl-functional groups; Way. 25. The method according to any one of claims 14 to 17 and 21 to 24, further comprising in step 1) G) adding an endblocker. A compound of the formula:

(wherein each R ⁸ is an independently selected monovalent hydrocarbon group of 1 to 18 carbon atoms; each R ⁹ is independently selected from the group consisting of hydrogen and an alkyl group of 1 to 15 carbon atoms; R ¹⁰ is an alkyl group of 1 to 8 carbon atoms and the subscript x is 1 or 2). 27. The compound of claim 26, wherein each R ⁸ is an independently selected alkyl group of 1 to 18 carbon atoms, each R ⁹ is hydrogen, and R ¹⁰ is methyl or ethyl. Unit formula: [(H ₂ NCH ₂ CH ₂ CH)R ⁸ ₂ SiO _1/2 ] _J [(H ₂ NCH ₂ CH ₂ CH)R ⁸ SiO _2/2 ] _K [(H ₂ NCH ₂ CH ₂ CH) SiO _3/2 ] _L (R ²⁰ ₃ SiO _1/2 ) _G (R ²⁰ ₂ SiO _2/2 ) _H (R ²⁰ SiO _3/2 ) _F (SiO _4/2 ) _D (wherein each R ⁸ is is an independently selected monovalent hydrocarbon group of 1 to 18 carbon atoms, each R ²⁰ is independently selected from the group consisting of a hydrolysable group and R ⁸ , a subscript J ≥ 0, a subscript K ≥ 0, a subscript L ≥ 0, subscript G ≥ 0, subscript H ≥ 0, subscript F ≥ 0, subscript D ≥ 0, quantity (J + K + L) > 1, quantity (L + F + D) > 1, and , wherein the quantity (J + K + L + G + H + F + D) has a value sufficient to provide the resin with Mn of 1,000 g/mol to 8,000 g/mol) of a primary-amino-functional polyol Organosiloxane resin. 29. The resin of claim 28, wherein each R ⁸ is independently selected from the group consisting of alkyl and aryl, and each R ²⁰ is independently selected from the group consisting of hydroxyl, alkyl and aryl. 30. The resin of claim 29, wherein each R ⁸ is independently selected from the group consisting of methyl and phenyl, and each R ²⁰ is independently selected from the group consisting of hydroxyl, methyl and phenyl. A cyclic polysiloxazane having the general formula:

(wherein each R ⁸ is an independently selected monovalent hydrocarbon group of 1 to 18 carbon atoms; each R ⁹ is an independently selected alkyl group of 1 to 15 carbon atoms). A cyclic polysiloxazane having the general formula:

(wherein each R ⁸ is an independently selected monovalent hydrocarbon group of 1 to 18 carbon atoms; each R ⁹ is independently selected from the group consisting of hydrogen and an alkyl group of 1 to 15 carbon atoms). 33. The cyclic polysiloxazane of claim 32, wherein each R ⁹ is hydrogen. 34. The cyclic polysiloxazane of any one of claims 31-33, wherein each R ⁸ is methyl.

,

,

,

, and

A cyclic polysiloxazane selected from the group consisting of.